CN104311450A

CN104311450A - Bis-schiff base sensor capable of circulation monitoring of copper ions, synthesis and applications thereof

Info

Publication number: CN104311450A
Application number: CN201410489493.XA
Authority: CN
Inventors: 魏太保; 李辉东; 张有明; 林奇; 姚虹
Original assignee: Northwest Normal University
Current assignee: Northwest Normal University
Priority date: 2014-09-23
Filing date: 2014-09-23
Publication date: 2015-01-28
Anticipated expiration: 2034-09-23
Also published as: CN104311450B

Abstract

According to the present invention, a bis-schiff base sensor capable of circulation monitoring of copper ions is designed and synthesized, and belongs to the field of cation detection. According to the bis-schiff base sensor, the sensor can perform high selectivity colorimetric fluoresce identification on Cu<2+> in a DMSO-H2O system, wherein the color and the fluoresce of the system are significantly changed when the Cu<2+> is added to the system while the addition of other cations does not cause the significant effect on the system, and when the DMSO-H2O system of the sensor is added with the Cu<2+> solution and then is added with H2PO4<->, the fluoresce of the system can be restored (at least cycles 5 times), such that the bis-schiff base sensor is the good and recycled Cu<2+> sensor. In order to rapid detection of copper ions, the bis-schiff base sensor is loaded on the test paper so as to prepare the copper ion detection test paper.

Description

A kind of bis-Schiff base sensor of monitoring cupric ion capable of circulation and synthesis thereof and application

Technical field

The invention belongs to cation detection field, relate to a kind of cupric ion acceptor compound; Particularly relate to the bis-Schiff base sensor of a kind of highly selective colorimetric-fluorescence two channels identification cupric ion.The present invention also relates to the synthesis of this cupric ion bis-Schiff base sensor simultaneously and is identifying the application in cupric ion.

Background technology

?it is special that metallic cation plays a part in the metabolic process of organism, and it is complete under the control in conjunction with respective egg white matter in the transmission of intraor extracellular.Ca ²⁺, Mg ²⁺deng in nerve conduction, play very important role in cell signaling processes, and a series of hypertoxic heavy metal such as lead, mercury, cadmium in metal is widely used in industrial process stream, they mostly finally change into positively charged ion and are discharged into nature.These heavy metal ion can be got up by enrichment in biological tissue by food chain, are converted into positively charged ion free in human body cell, also play an important role, thus cause tremendous influence to Man & Nature circle in the physiological process of biology.Therefore, it is possible to effectively detecting these metallic cations in cell has great meaning for biological chemistry, 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.Cu ²⁺excessive, not only can contaminate environment, if too much at people's cylinder accumulation, much serious disease can be caused.Given this, cupric ion conveniently detects the extensive concern causing people, and constantly inquires into its detection method.

In numerous cations recognition system, schiff bases is the very important host molecule of a class.Schiff bases is the compounds that a class contains imido grpup (C=N).Research shows, schiff bases and title complex thereof have important effect in fields such as spectroscopy, coordination chemistry, analytical chemistry.But the application for schiff bases Selective recognition cupric ion has not yet to see report.

Summary of the invention

The object of this invention is to provide a kind of can the bis-Schiff base sensor of highly selective colorimetric-fluorescence identifying cupric ion;

Another object of the present invention is to provide a kind of synthetic method of ion bis-Schiff base sensor of above-mentioned colorimetric-fluorescence identifying copper;

A further object of the invention is just to provide the embody rule of above-mentioned colorimetric-fluorescence identifying cupric ion bis-Schiff base sensor.

One, bis-Schiff base sensor and synthesis thereof

The ion bis-Schiff base sensor (L) of colorimetric of the present invention-fluorescence two channels identification copper, its structural formula is as follows:

The synthesis of bis-Schiff base sensor: solvent made by dehydrated alcohol, catalyzer made by Glacial acetic acid, and 2-hydroxyl-1-naphthalene Formaldehyde and adjacent first p-diaminodiphenyl, with the mol ratio of 1.5:1 ~ 1.0:1, react 10 ~ 12h, obtain yellow solid at 85 ~ 90 DEG C.

The consumption of catalyzer Glacial acetic acid is 1.5 ~ 2.0% of adjacent first p-diaminodiphenyl molar weight.

The characterization data of above-mentioned synthetic product is 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 cupric ion

1. pair cationic ultraviolet compares colour discrimination

L DMSO is made into 2 × 10 ^-4the bulk solution of mol ∕ L; The bulk solution getting 0.5mL respectively, in 13 colorimetric cylinders, adds the different positively charged ion (Fe of 0.25mL respectively ³⁺, Hg ²⁺, Ag ⁺, Ca ²⁺, Cu ²⁺, Co ²⁺, Ni ²⁺, Cd ²⁺, Pb ²⁺, Zn ²⁺, Cr ³⁺, Mg ²⁺) the DMSO solution (10eqv) of perchlorate, then add 1mLpH=7.2 buffered soln (water of the pH=7.2 become with TBAH regulating allocation by 4-hydroxyethyl piperazine ethanesulfonic acid) successively, finally with DMSO constant volume to 5mL, mix rear standing.Now the concentration of sensor is 2 × 10 ^-5mol/L, the percent by volume 20% of water in system.Found that: only have Cu ²⁺add and make the color of bulk solution become light green from yellow, and other cationicly adds, and makes the color of bulk solution become orange from yellow.In corresponding uv-vis spectra, Cu ²⁺add and make bulk solution occur obvious blue shift at 450nm place respectively, and other cationic adding has no significant effect (see figure 1) to the UV spectrum of bulk solution.Illustrate that bis-Schiff base sensor L can colorimetric detection Cu in the mixed system of DMSO and water ²⁺.

2, ultraviolet titration

Below by the binding constant of UV Vis titration experimental study sensor L and cupric ion.L DMSO is made into 2 × 10 ^-4the bulk solution of mol ∕ L, adds 2mL buffered soln (water of the pH=7.2 become with TBAH regulating allocation by 4-hydroxyethyl piperazine ethanesulfonic acid), with DMSO constant volume to 10mL, shakes up standing.Add the DMSO solution of the perchlorate of cupric ion.Find to increase gradually along with copper ion concentration in system, UV spectrum declines gradually at peak, 480nm place, and raises gradually at the peak at 425nm place.There is obvious blue shift in peak, meanwhile, has occurred 3 isobestic points at 350,380,440nm place, shows that this titration process defines stable complex compound (see Fig. 2, wherein illustration is the scatter diagram going out absorbancy reduction at 486nm).From Fig. 2 can be clear and definite find out L and Cu ²⁺coordination ratio be 1:2.

3, to cationic fluoroscopic examination identification

L DMSO is made into 2 × 10 ^-4the bulk solution of mol ∕ L; The bulk solution getting 0.5mL respectively, in 13 colorimetric cylinders, adds the different positively charged ion (Fe of 0.25mL respectively ³⁺, Hg ²⁺, Ag ⁺, Ca ²⁺, Cu ²⁺, Co ²⁺, Ni ²⁺, Cd ²⁺, Pb ²⁺, Zn ²⁺, Cr ³⁺, Mg ²⁺) the DMSO solution (50eqv) of perchlorate, then add 1mLpH=7.2 buffered soln (water of the pH=7.2 become with TBAH regulating allocation by 4-hydroxyethyl piperazine ethanesulfonic acid) successively, finally use DMSO constant volume is to 5mL.Then use the ultra violet lamp of 365nm, find Fe ³⁺, Hg ²⁺, Ag ⁺, Ca ²⁺, Co ²⁺, Ni ²⁺, Cd ²⁺, Pb ²⁺, Zn ²⁺, Cr ³⁺, Mg ²⁺add on the fluorescence of L all without impact, and Cu ²⁺after adding, the complete quencher of strong green fluorescence of bulk solution.Meanwhile, as can be seen from fluorescent emission figure (Fig. 3), in bulk solution, Cu is added ²⁺, its hyperfluorescenceZeng Yongminggaoyingguang emission peak at 530nm place disappears, and adds all the other positively charged ions, and it all occurs very strong emission peak at 530nm place.Illustrate that sensor L can at DMSO(moisture 20%) in sensitive detection Cu single-minded fast ²⁺.

4, the mensuration of lowest detectable limit

25 DEG C time, utilize uv-vis spectra, according to Cu ²⁺to the titration experiments of receptor solution, pass through 3s _b/ S calculates, and can obtain L to Cu ²⁺lowest detectable limit reach 7.25 × 10 ^-8molL ¹.

5, fluorescence interference--free experiments

Fig. 4 is acceptor l(2 × 10 ^-4molL ^-1) in DMSO (moisture 20%) solution to Cu ²⁺the anti-interference figure of fluorescence of ion.As seen from Figure 4, acceptor L identifies Cu ²⁺not by the impact of other ions, therefore anti-interference energy is fabulous, and show that acceptor L can under other coexisting ion exists, interference-free highly selective detects Cu ²⁺.

6, reusable edible performance

In order to study acceptor L and Cu ²⁺in conjunction with situation, further probing into of fluorometric titration is carried out to it.Along with Cu ²⁺add gradually, 530nm place fluorescence emission peak reduces gradually, finally, when adding the Cu of 14 equive ²⁺time, this emission peak completely dissolve.When to the Cu adding 14 equive ²⁺solution in add the H of 28 equive ₂pO ₄ ^-time, fluorescence recovers again, like this energy well reciprocation cycle 5 times (Fig. 5), and therefore, L is a kind of Cu of good reusable edible ²⁺sensor.

Great many of experiments shows, at DMSO-H ₂in O system, H ₂the percent by volume of O is 15 ~ 20% time, and bis-Schiff base sensor L is at DMSO-H ₂fluorescence-colorimetric the recognition performance to cupric ion can be realized in O system.

Three, Cu ²⁺test paper and application

For the ease of detecting Cu ²⁺, we have prepared load sensor L and L-Cu ²⁺test paper: the filter paper dilute hydrochloric acid of 0.5 mol/L is soaked 1 hour, then with distilled water wash repeatedly, till filtrate is neutrality.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 dissolution homogeneity of L be adsorbed on filter paper; Then be placed in vacuum drying oven dry, obtain the test paper that load has sensor L.This Test paper, under visible light in safran, is green under 365nm ultraviolet lamp.Drip Cu ²⁺after, this Test paper is light green under visible light, quenching of fluorescence under ultraviolet lamp; After dripping other positively charged ion, test paper color is substantially constant.

Accompanying drawing explanation

Fig. 1 is l(2 × 10 ^-4molL ^-1) in DMSO (moisture 20%) solution to cationic ultraviolet-visible absorption spectroscopy figure; Fig. 2 is l(2 × 10 ^-4molL ^-1) in DMSO (moisture 20%) solution and solution to Cu ²⁺the ultraviolet titration figure of ion.

Fig. 3 is l(2 × 10 ^-4molL ^-1) in DMSO (moisture 20%) solution to cationic fluorescent emission figure.

Fig. 4 acceptor l(2 × 10 ^-4molL ^-1) in DMSO (moisture 20%) solution to Cu ²⁺the anti-interference figure of fluorescence of ion.

Fig. 5 acceptor l(2 × 10 ^-4molL ^-1) in DMSO (moisture 20%) solution to Cu ²⁺-H ₂pO ₄ ^-the fluorescence of ion opens the light figure.

Embodiment

Below by specific embodiment to structure, the synthesis of sensor L of the present invention and be described in detail the detection recognition methods of cupric ion, the Synthesis and applications of Test paper.

1, the synthesis of sensor molecule L

Taking 0.48g(2.4mmol) 2-hydroxyl-1-naphthalene Formaldehyde is placed in the round-bottomed flask of 100mL, add 40mL dehydrated alcohol and make solvent, slowly 0.45g(2mmol is added under stirring) adjacent first p-diaminodiphenyl, catalyzer made by 1mL Glacial acetic acid, stirred at ambient temperature 30min, then be placed in 85 DEG C of oil bath pans to reflux 12h, obtain yellow solid 1.06g.Productive rate 80%.

2, the preparation of Test paper

Filter paper is cut into the square of 8 cm × 8 cm, uses 0.5 molL ^-1dilute hydrochloric acid soak 1 hour.With distilled water wash repeatedly after, limit suction strainer limit distilled water wash on a buchner funnel, till filtrate is neutrality.Washed filter paper, except anhydrating, is placed in vacuum drying oven dry by suction strainer.Be dissolved in DMSO solution by sensor L, being mixed with concentration is 2.0 × 10 ^-4molL ^-1dMSO solution.The filter paper handled well is lain against in 10cm plate, drip DMSO solution with dropper in the central position of filter paper, make filter paper uniform adsorption DMSO solution.After being placed in vacuum drying oven drying, being cut into the test strip of 0.5 cm × 4 cm, being placed in clean, dry containers for future use.This Test paper, under visible light in safran, is green under 365nm ultraviolet lamp.

3, the detection of cupric ion

By Fe ³⁺, Hg ²⁺, Ag ⁺, Ca ²⁺, Cu ²⁺, Co ²⁺, Ni ²⁺, Cd ²⁺, Pb ²⁺, Zn ²⁺, Cr ³⁺, Mg ²⁺dMSO(2 × 10 of perchlorate ^-4molL ^-1) be added drop-wise to respectively on copper ion test paper.Under visible light, if test paper color becomes light green from safran, under the ultraviolet lamp of 365nm, test paper color is by green to quenching of fluorescence, and that dropping is described is Cu ²⁺; If test paper color color under the ultraviolet of visible ray and 365nm does not all have considerable change, then illustrate that dripping room temperature is other positively charged ion.

Claims

1. a bis-Schiff base sensor for detection cupric ion capable of circulation, its structural formula is as follows:

。

2. the synthetic method of the bis-Schiff base sensor of detection cupric ion capable of circulation as claimed in claim 1, be make solvent with dehydrated alcohol, catalyzer made by Glacial acetic acid, and 2-hydroxyl-1-naphthalene Formaldehyde and adjacent first p-diaminodiphenyl are with the mol ratio of 1.5:1 ~ 1.0:1, at 85 ~ 90 DEG C, react 10 ~ 12h, obtain yellow solid.

3. the synthetic method of the bis-Schiff base sensor of detection cupric ion capable of circulation as claimed in claim 1, is characterized in that: the consumption of catalyzer Glacial acetic acid is 1.5 ~ 2.0% of adjacent first p-diaminodiphenyl molar weight.

4. as claimed in claim 1 the bis-Schiff base sensor of detection cupric ion capable of circulation at DMSO-H ₂the application of cupric ion is detected in O system.

5. as claimed in claim 4 the bis-Schiff base sensor of detection cupric ion capable of circulation at DMSO-H ₂detect the application of cupric ion in O system, it is characterized in that: at DMSO-H ₂in O system, only has Cu ²⁺add and make the color of system become light green from yellow, and other cationicly adds, and makes the color of system become orange from yellow.

6. as claimed in claim 4 the bis-Schiff base sensor of detection cupric ion capable of circulation at DMSO-H ₂detect the application of cupric ion in O system, it is characterized in that: at DMSO-H ₂in O system, only has Cu ²⁺add and make the complete quencher of the fluorescence of system, and other cationic adding has no significant effect the fluorescence of system.

7. as described in claim 4-6 the bis-Schiff base sensor of detection cupric ion capable of circulation at DMSO-H ₂detect the application of cupric ion in O system, it is characterized in that: DMSO-H ₂in O system, H ₂the percent by volume of O is 15 ~ 20%.

8. a load has the Test paper of the bis-Schiff base sensor of detection cupric ion capable of circulation as claimed in claim 1.

9. as claimed in claim 8 the test paper of the bis-Schiff base sensor of detection cupric ion capable of circulation for detecting the method for cupric ion, by Fe ³⁺, Hg ²⁺, Ag ⁺, Ca ²⁺, Cu ²⁺, Co ²⁺, Ni ²⁺, Cd ²⁺, Pb ²⁺, Zn ²⁺, Cr ³⁺, Mg ²⁺be added drop-wise on Test paper respectively, if test paper color becomes light green from safran under visible light, that dropping is described is Cu ²⁺; If the color of test paper color does not have considerable change, then what dropping was described is other positively charged ion.

10. as claimed in claim 8 the test paper of the bis-Schiff base sensor of detection cupric ion capable of circulation for detecting the method for cupric ion, by Fe ³⁺, Hg ²⁺, Ag ⁺, Ca ²⁺, Cu ²⁺, Co ²⁺, Ni ²⁺, Cd ²⁺, Pb ²⁺, Zn ²⁺, Cr ³⁺, Mg ²⁺be added drop-wise on Test paper respectively, if the color of test paper under ultraviolet lamp becomes quenching of fluorescence from very strong green fluorescence, that dropping is described is Cu ²⁺; If test paper color does not have considerable change under ultraviolet, then what dropping was described is other positively charged ion.