CN106632101B - A kind of Ratiometric fluorescent probe and the preparation method and application thereof that can be used for silver ion and trivalent chromic ion detection simultaneously - Google Patents
A kind of Ratiometric fluorescent probe and the preparation method and application thereof that can be used for silver ion and trivalent chromic ion detection simultaneously Download PDFInfo
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Abstract
The invention discloses the Ratiometric fluorescent probes and the preparation method and application thereof that one kind can be used for silver ion and trivalent chromic ion detection simultaneously.The fluorescence probe is the symmetrical structure of double the pyrene rings and triazole of triethylene glycol connection, is existed when being not detected among ion in system, and in the transmitting light excitation of specific wavelength, system issues the characteristic fluorescence transmitting band of the excimer of pyrene；When being separately added into silver ion and trivalent chromic ion in system, two kinds of tested measured ions form the complex compound of specific structure from recognition group by different interactions, destroy the excimer structure of probe molecule, so as to realize the Ratio-type fluorescence detection to silver ion and trivalent chromic ion respectively, the interference of external condition can be avoided in analysis detection.Fluorescence probe of the invention visually differentiates the different responses to silver ion and trivalent chromic ion under being irradiated in buffer with hand-held ultraviolet lamp, and is expected to be used for the quantitative analysis of silver ion and trivalent chromic ion in the samples such as chemistry, environment.
Description
Technical field
The present invention relates to a kind of fluorescent probe compounds, more particularly to one kind can be used for simultaneously silver ion and trivalent chromium from
The Ratiometric fluorescent probe and the preparation method and application thereof of son detection, belongs to technical field of analysis and detection.
Background technique
Transition metal and heavy metal are widely present in nature, are had very important significance to the maintenance ecological balance.
Chromium is one of the essential trace elements of the human body, develops to human normal and adjusting blood glucose plays an important role, when human body lacks chromium,
It will appear glycometabolism imbalance, serious person can be with diseases such as diabetes, uremias；On the contrary, if human body intake chromium content is excessively high
Words, then can cause the lesion of kidney, liver and nervous system；Industrially, chromium can be plated on metal for the anti-of metal
Rust；Meanwhile chromium can also be used to produce sodium dichromate, and then produce other chromium compounds, be used for pigment, weaving, plating, process hides
Etc. industries.The discharge of a large amount of waste water, exhaust gas enters chromium in nature in the form of an ion in these industries, to ecological environment and people
Health cause very big threat.Meanwhile silver ion as electronic apparatus material, photosensitive material and chemical material in work
It is widely used in industry, consequent is silver ion pollution；Silver is used as heavy metal, has bioaccumulation, people
Body intake is excessive, can make the enzyme inactivation with sulfydryl in vivo and then influence the metabolism of human body.In fact, in industrial wastewater, giving up
Various metals ion in gas and physiological environment often including silver ion and chromium ion etc. exists simultaneously, therefore can be same
When the exceeded silver ion and trivalent chromic ion that fast and accurately detects in environment be of great significance.
Currently, carried out a large amount of research to the detection of silver ion and trivalent chromic ion both at home and abroad, common silver ion and
The detection method of trivalent chromic ion mainly has electrochemical methods, colorimetric method and fluorescence method.Electrochemical methods are for detecting silver
Ion (such as 103630585 A of patent CN) can mainly be significantly increased using the AgBr nanoparticle based on growth in situ
The optical electro-chemistry sensing responsive degree of ZnO nano-rod array, detected by the method for photocurrent-time various concentration silver from
Son；But the interference vulnerable to other reproducibilities or oxidizing substance present in sample of electrochemical method, therefore the standard detected
True property is difficult to ensure.Colorimetric method for detect trivalent chromic ion (such as the J.Chin.Chem.Soc.2014,61 that publishes thesis,
1395-1399), it is prepared for the gold nanoparticle that surface modification has ethylenediamine tetra-acetic acid, under the action of trivalent chromic ion, gold
Nanoparticle can be assembled, and the surface plasma absorption of solution changes, while the color of solution becomes purple from red
Color, to realize the detection to trivalent chromic ion；But colorimetric method is higher to the purity requirement of sample, is disturbed more serious.
Fluorescence method has many advantages, such as that synthesis is simple, high sensitivity, specificity are good, identification responsiveness is fast in analysis detection, is suitble to gold
Belong to the analysis detection of ion.However Fluorometric assay silver ion and trivalent chromic ion conventional at present be mainly fluorescence enhancement type and
Fluorescent quenching type.These methods vulnerable to interference (such as fluorescence enhancement impurity or quencher etc. present in sample concentration, sample),
Therefore, it is difficult to ensure the accuracy of detection.For example, the method for fluorescence enhancement type detection trivalent chromic ion (such as publishes thesis
Tetrahedron Letters 2014,55,351-353), it has synthesized and a kind of has been connected with two formyl of naphthalene on No. 2 positions of dinaphthol
The fluorescence probe of imine derivative；The probe sends out hypofluorescence because of photo induced electron transfer at 491nm, and trivalent chromic ion is added
Afterwards, photo induced electron transfer is cut off, is greatly enhanced its fluorescence at 498nm, to realize to the glimmering of trivalent chromic ion
The enhanced detection of light.Fluorescent quenching type detects the method (such as 104610228 A of patent CN) of trivalent chromic ion, synthesis
2- (1- (pyridine -2- ylmethoxy) pyrans -2- base) this fluorescence probe of 1H phenanthro- [9,10-D] azoles；The probe is at 434nm
Hyperfluorescence is sent out, trivalent chromic ion is added, fluorescence intensity is obviously reduced, to realize the fluorescent quenching type inspection to trivalent chromic ion
It surveys.In addition, the probe with response identification function that is multiduty and can be achieved at the same time various metals ion is in practical application
In have great importance, so far, the fluorescent detection system of silver ion and trivalent chromic ion can be detected simultaneously not yet
Report.
Therefore this field is badly in need of a kind of strong antijamming capability, high sensitivity, can identify silver ion and trivalent chromium simultaneously
The analyzing detecting method of ion.
Summary of the invention
Technical problem to be solved by the invention is to provide one kind can be used for simultaneously silver ion and trivalent chromic ion detection
Ratiometric fluorescent probe and the preparation method and application thereof, for the present invention using two pyrene rings as fluorophor, triazole and oxygen atom are to know
Other group；By silver ion and the trivalent chromic ion combination different from recognition group, two kinds of different stereochemical structures are formed
Complex compound, to realize the Ratio-type fluorescent detection probe responded to silver ion with trivalent chromic ion difference.
The object of the invention is achieved through the following technical solutions.
A kind of Ratiometric fluorescent probe that can be used for silver ion and trivalent chromic ion detection simultaneously, the fluorescence probe are
(((ethane -1,2- diyl is bis- (oxygroup)) are bis- (ethane -2,1- diyl)) are bis- (1H-1,2,3- triazole -1,4- diyl)) bis- (methylenes
Base) bis- (pyrene -1- carboxylic acids), structural formula is as follows:
Prepare the Ratiometric fluorescent probe that above-described one kind can be used for silver ion and trivalent chromic ion detection simultaneously
Method comprising the steps of:
1) bis- (the 2- nitrine base oxethyl) ethane of 1- pyrene formic acid -1- propynyl ester and 1,2- are dissolved in tetrahydrofuran；
2) Salzburg vitriol is added and ascorbic acid sodium water solution, reaction temperature is room temperature, react 20-24 hours；
3) it after rotary evaporation removes tetrahydrofuran, is extracted with ethyl acetate/deionized water, collects organic phase, will have
Machine is mutually washed with brine, and is dried, filtered；Rotary evaporation removing organic solvent, obtained solid by silica gel chromatography column purification, consolidate
Body fluorescence probe, i.e. (((ethane -1,2- diyl is bis- (oxygroup)) are bis- (ethane -2,1- diyl)) bis- (1H-1,2,3- triazoles-Isosorbide-5-Nitraes -
Diyl)) bis- (methylene) bis- (pyrene -1- carboxylic acid).
Preferably, step 1) the 1- pyrene formic acid -1- propynyl ester the preparation method is as follows: 1- pyrene formic acid is dissolved in N, N- bis-
In methylformamide, 3- propargyl bromide and potassium carbonate is added, controls reaction temperature at 80-105 DEG C, is stirred to react 5-7 hours；It is cooling
To room temperature, deionized water is added, is then extracted with ethyl acetate；Organic phase is collected, organic phase is washed with brine, with nothing
Aqueous sodium persulfate dries, filters；Rotary evaporation removes organic solvent, and obtained solid by silica gel chromatography column purification obtains solid 1- pyrene
Formic acid -1- propynyl ester.
It is further preferred that the molar ratio of the 1- pyrene formic acid and 3- propargyl bromide is 1:1.5-1:2.5；The 1- pyrene formic acid
Molar ratio with potassium carbonate is 1:(1.5-3.5)；N,N-dimethylformamide 1-2.5mL is added in every mmol 1- pyrene formic acid.
It is further preferred that the salt water is the sodium chloride solution of mass percentage concentration 5%.
Preferably, bis- (the 2- nitrine base oxethyl) ethane of step 1) 1, the 2- the preparation method is as follows: triethylene glycol is put
In a vacuum drying oven 95-120 DEG C it is 2-3 hours dry, be then dissolved in methylene chloride, triethylamine and 4- dimethylamino be added
P-methyl benzene sulfonic chloride is added under condition of ice bath for pyridine, stirs 0.5-1.5 hours, removes ice bath, the reaction was continued at room temperature 3-
8 hours；Deionized water is added, is extracted, collects organic phase, organic phase is washed with brine, mistake dry with anhydrous sodium sulfate
Filter, rotary evaporation remove organic solvent, and obtained solid by silica gel chromatography column purification obtains solid 1, bis- (the 2- tosyls of 2-
Ethyoxyl) ethane；Bis- (the 2- tosyl base oxethyl) ethane of 1,2- are dissolved in n,N-Dimethylformamide, Azide is added
Sodium controls reaction temperature at 80-105 DEG C, is stirred to react 4-6 hours, normal-temperature reaction 15-24 hours later, adds deionization
Then water is extracted with ethyl acetate；Organic phase is collected, organic phase is washed with brine, is dried, filtered with anhydrous sodium sulfate；
Rotary evaporation removes organic solvent, and obtained solid by silica gel chromatography column purification obtains solid 1,2- bis- (2- nitrine base oxethyls)
Ethane.
It is further preferred that methylene chloride 15-20mL is added in every mmol triethylene glycol；Mole of the triethylene glycol and triethylamine
Than for 1:1-1:1.2；The molar ratio of the triethylene glycol and 4-dimethylaminopyridine is 1:3-1:4.2；The triethylene glycol with it is right
The molar ratio of toluene sulfonyl chloride is 1:2.8-1:5；N, N- is added in every bis- (2- tosyl base oxethyl) ethane of mmol 1,2-
Dimethylformamide 10-15mL；The molar ratio of bis- (the 2- tosyl base oxethyl) ethane of the 1,2- and sodium azide is 1:
2-1:3。
It is further preferred that the salt water is the sodium chloride solution of mass percentage concentration 5%.
Preferably, in step 1), tetrahydrofuran 10-25mL is added in bis- (the 2- nitrine base oxethyl) ethane of every mmol 1,2-；
The molar ratio of bis- (the 2- nitrine base oxethyl) ethane of 1,2- and 1- pyrene formic acid -1- propynyl ester is 1:2.5-1:3.
Preferably, the molar ratio of the step 2) Salzburg vitriol and sodium ascorbate is 1:2-1:3.2；Five water
The molar ratio for closing copper sulphate and bis- (the 2- nitrine base oxethyl) ethane of 1,2- is 1:10-1:22.
Preferably, drying described in step 3) is to be dried with anhydrous sodium sulfate；The salt water is that quality percentage is dense
Degree is the sodium chloride solution of 5%-10%.
Above-described Ratiometric fluorescent probe is applied to while identifying in the detection of silver ion and trivalent chromic ion.
(((ethane -1,2- diyl is bis- (oxygroup)) are bis- (ethane -2,1- diyl)) are double for products therefrom fluorescence probe of the present invention
(1H-1,2,3- triazoles-Isosorbide-5-Nitrae-diyl)) bis- (methylene) bis- (pyrene -1- carboxylic acid), molecular formula C46H36N6O6, molecular weight is
768.3.The fluorescence probe is red brown solid, is slightly soluble in water, is soluble in the organic solvents such as dimethyl sulfoxide；The chemical combination object light is steady
It is qualitative preferable, it is nontoxic, there is good biocompatibility.The structure of the probe compound is symmetrical by the pyrene ring of triethylene glycol connection
Structure, two of them pyrene ring are fluorophor, and two triazoles and oxygen atom are recognition group；Two pyrene rings pass through pi-pi accumulation
Forming excimer has a stronger excimer at the place 515nm or so under the excitation of 345nm wavelength
Yellow-green fluorescence.After silver ion is added, recognition group (triazole) and silver ion complexation increase the distance of two pyrene units
Greatly, the amount of excimer is reduced, and the fluorescence of excimer also accordingly weakens；And the quantity of pyrene monomer increases, it is corresponding
Blue-fluorescence gradually increases；After trivalent chromic ion is added in system, recognition group (triazole and oxygen atom) and trivalent chromic ion
In conjunction with the excimer structure formed centered on trivalent chromic ion, system occurs under the exciting light irradiation of 345nm wavelength
Intramolecular energy, so that excimer has been quenched and has existed in the energy transfer to trivalent chromic ion of the excimer of pyrene
Fluorescence at 515nm.Therefore, fluorescence probe according to the present invention can form different networks from silver ion and trivalent chromic ion
The Ratio-type fluorescence detection to silver ion and trivalent chromic ion can be realized respectively, be expected to use by different interactions by closing object
The quantitative analysis of silver ion and trivalent chromic ion in the samples such as biochemical, biological, environment.
Compared with the prior art, the invention has the advantages that and technical effect:
(1) structure for the probe compound that the present invention synthesizes is the two pyrene unit symmetrical structures connected by triethylene glycol,
In two pyrene rings as fluorophor, two triazoles and oxygen atom are as different recognition groups；Two pyrene rings pass through π-π heap
Product effect forms excimer, and by the variation of fluorophor pyrene monomer stereochemical structure, system can emit monomer fluorescence and swash
Ground state fluorescence, so as to be used for Ratio-type fluorescence detection.
(2) fluorescence probe that the present invention synthesizes has a weaker pyrene list under 345nm excitation at 420nm
Body fluorescence has the yellow-green fluorescence of a stronger excimer in 515nm or so.After silver ion is added, recognition group
(triazole) destroys the excimer structure of pyrene in conjunction with silver ion, and fluorescence of the system at 515nm gradually weakens；And pyrene
The quantity of unit increases, so that blue-fluorescence enhancing of the system at 420nm, to carry out the inspection of Ratio-type fluorescence to silver ion
It surveys；In the presence of trivalent chromic ion, chromium ion and triazole and oxygen atom form complex compound, under the excitation of 345nm,
Energy transfer occurs in system, fluorescence of the excimer at 515nm has been quenched, and the fluorescence of pyrene monomer is kept at 420nm
It is constant.Using the ratio of the fluorescence intensity of monomer fluorescence and excimer as detection signal, to realize to trivalent chromic ion
Ratio-type fluorescence detection.This system detects influence of the unrelated external factor of identification events to the fluorescence signal intensity of the two
Consistent, so something outside is difficult to influence the ratio of two kinds of fluorescence intensities, this mode can greatly reduce external factor
Influence, improve detection accuracy and accuracy.
(3) fluorescence probe that the present invention synthesizes passes through different recognition groups and the phase between silver ion and trivalent chromic ion
Interaction, being formed, there is the complex system of different stereochemical structures can be realized respectively using the special mechanism of fluorescence emission of pyrene unit
Ratio-type fluorescence detection to silver ion and trivalent chromic ion；And fluorescence probe of the present invention can shine in hand-held ultraviolet lamp
Lower naked eyes resolution is penetrated to respond silver ion and the different of trivalent chromic ion；Detection architecture according to the present invention is more traditional only to be examined
The method surveyed silver ion or only detect trivalent chromic ion is time saving and energy saving.
Detailed description of the invention
Fig. 1 is the synthetic route chart of fluorescence probe of the present invention.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of 1- pyrene formic acid -1- propynyl ester in embodiment 1.
Fig. 3 is (((ethane -1,2- diyl is bis- (oxygroup)) are bis- (ethane -2,1- diyl)) bis- (1H-1,2,3- in embodiment 1
Triazole -1,4- diyl)) hydrogen nuclear magnetic resonance spectrogram of bis- (methylene) bis- (pyrene -1- carboxylic acids).
The structure for the different complexes to be formed is complexed for the fluorescence probe in the present invention with silver ion and trivalent chromic ion by Fig. 4
Figure.
Fig. 5 is for the fluorescence probe in the present invention in silver ion and trivalent chromic ion and other metals in Tris buffer
Fluorescence spectra in the presence of ion.
Fig. 6 be the present invention in fluorescence probe in Tris buffer in the presence of silver ion and trivalent chromic ion
Fluorescence intensity ratio variation diagram at 420nm and 515nm.
After Fig. 7 is separately added into silver ion and trivalent chromic ion for the fluorescence probe in the present invention in Tris buffer,
Hand-held ultraviolet lamp irradiates the fluorescence photo under (365nm).
Specific embodiment
Specific implementation of the invention is further described below in conjunction with drawings and examples, but the present invention claims guarantors
The range of shield is not limited to the scope of the embodiments.
Embodiment 1: the preparation process flow 1 of fluorescence probe
1) it takes 186mg 1- pyrene formic acid (0.75mmol) to be dissolved in 0.75mL n,N-Dimethylformamide, 132mg is added
3- propargyl bromide (1.125mmol) and 154mg potassium carbonate (1.125mmol) control reaction temperature at 80 DEG C, are stirred to react 5 hours；
It is cooled to room temperature, adds 20mL deionized water, extracted with 100mL ethyl acetate, collect organic phase, organic phase salt water
(50g/L) washing, is dried, filtered with 100mg anhydrous sodium sulfate；Rotary evaporation removes organic solvent, and obtained solid is through layer of silica gel
Analysis column purification (eluent are as follows: petroleum ether/methylene chloride, V/V=4:1) obtains white solid 1- pyrene formic acid -1- propynyl ester (yield
For 93.0%)；Product is characterized by nuclear magnetic resonance1H NMR(CDCl3,600MHz,δppm):9.28-9.30(d,1H),
8.65-8.70(d,1H),8.23-8.28(q,3H),8.15-8.19(t,2H),8.04-8.09(q,2H),5.11-5.13(d,
2H),2.58-2.60(t,1H).Wherein 9.28ppm, 8.65ppm, 8.23ppm, 8.15ppm, 8.04ppm represent the matter on pyrene ring
The characteristic peak of son, 5.11ppm represent the characteristic peak of proton on methylene, and 2.58ppm represents the feature of the proton on alkynyl
Peak.It can determine that synthesized product is title intermediate by the analysis of nuclear-magnetism.Hydrogen nuclear magnetic resonance spectrogram is as shown in Figure 2.
2) 434mg triethylene glycol (2.9mmol) dry 2 hours in 95 DEG C of baking ovens are taken, are dissolved in 43.5mL methylene chloride,
1.06g 4-dimethylaminopyridine (8.7mmol) and 400 μ L triethylamines (2.9mmol) are added, 1.55g is added under condition of ice bath
P-methyl benzene sulfonic chloride (8.1mmol) stirs 0.5 hour, removes ice bath, reacts 3 hours at room temperature；Be added 15mL go from
Sub- water, is extracted, and collects organic phase, organic phase is washed with salt water (50g/L), and the drying of 100mg anhydrous sodium sulfate, mistake is added
Filter, rotary evaporation remove organic solvent, obtained solid by silica gel chromatography column purification (eluent are as follows: methylene chloride/methanol, V/V=
9:1), solid 1, bis- (the 2- tosyl base oxethyl) ethane (yield 90.1%) of 2- are obtained.
Bis- (the 2- tosyl base oxethyl) ethane (1.0mmol) of 426mg 1,2- are taken to be dissolved in 10mL N, N- dimethyl methyl
In amide, add 130mg sodium azide (2mmol), controls reaction temperature at 80 DEG C, be stirred to react 4 hours, later normal-temperature reaction 15
Hour；20mL deionized water is added, is extracted with 100mL ethyl acetate, organic phase is collected, organic phase is with salt water (50g/L)
Washing, is dried, filtered with 100mg anhydrous sodium sulfate；Rotary evaporation removes organic solvent, obtained solid by silica gel chromatography column purification
(eluent is petrol ether/ethyl acetate, V/V=1:2), obtains product 1, and (yield is bis- (the 2- nitrine ethyoxyl) ethane of 2-
78.0%).
3) 23mg 1 is taken, bis- (the 2- nitrine base oxethyl) ethane (0.115mmol) of 2- are dissolved in 1.15mL tetrahydrofuran, add
Enter 81mg 1- pyrene formic acid -1- propynyl ester (0.288mmol), stirs 30 minutes, 0.4mL Salzburg vitriol solution is then added dropwise
(28.7mM) and 0.4mL sodium ascorbate solution (57mM) reacts 20 hours at room temperature；Rotary evaporation removes tetrahydrofuran
Afterwards, add 20mL deionized water, extracted with 100mL ethyl acetate, collect organic phase, organic phase is washed with salt water (50g/L)
It washs, dries, filters；Rotary evaporation removing organic solvent, obtained solid by silica gel chromatography column purification (eluent are as follows: methylene chloride/
Methanol, V/V=9:1), obtain solid (((ethane -1,2- diyl is bis- (oxygroup)) are bis- (ethane -2,1- diyl)) it is bis- (1H-1,2,
3- triazole -1,4- diyl)) bis- (methylene) bis- (pyrene -1- carboxylic acid) (yield 89.4%)；By nuclear magnetic resonance spectroscopy to product into
Row characterization (as shown in Figure 3),1H NMR(CDCl3, 600MHz, δ ppm): 9.15 (d, J=9.4Hz, 2H), 8.51 (d, J=
8.1Hz, 2H), 8.18-7.89 (m, 17H), 5.60 (s, 4H), 4.45 (t, J=5.0Hz, 4H), 3.71 (t, J=5.0Hz,
4H),3.44(s,4H).It can determine that synthesized product is fluorescence probe, synthetic route such as Fig. 1 institute by the analysis of nuclear-magnetism
Show.
Embodiment 2: the preparation process flow 2 of fluorescence probe
1) it takes 93mg 1- pyrene formic acid (0.375mmol) to be dissolved in 0.66mL n,N-Dimethylformamide, 88.4mg is added
3- propargyl bromide (0.75mmol) and 128mg potassium carbonate (0.94mmol) control reaction temperature at 92.5 DEG C, are stirred to react 6 hours；
It is cooled to room temperature, adds 10mL deionized water, extracted with 50mL ethyl acetate, collect organic phase, organic phase salt water (50g/
L it) washs, is dried, filtered with 50mg anhydrous sodium sulfate；Rotary evaporation removes organic solvent, and obtained solid by silica gel chromatography column is pure
Change (eluent are as follows: petroleum ether/methylene chloride, V/V=4:1) to obtain white solid 1- pyrene formic acid -1- propynyl ester (yield is
92.1%).
2) 217mg triethylene glycol (1.45mmol) dry 2.5 hours in 107.5 DEG C of baking ovens are taken, 25.4mL dichloro is dissolved in
In methane, it is added 0.66g 4-dimethylaminopyridine (5.22mmol) and 294 μ L triethylamines (2.18mmol), under condition of ice bath
It is added 0.78g p-methyl benzene sulfonic chloride (4.0mmol), stirs 1 hour, remove ice bath, react 5.5 hours at room temperature；Add
Enter 10mL deionized water, extracted, collect organic phase, organic phase is washed with salt water (50g/L), 50mg anhydrous slufuric acid is added
Sodium dries, filters, rotary evaporation removing organic solvent, obtained solid by silica gel chromatography column purification (eluent are as follows: methylene chloride/
Methanol, V/V=9:1), obtain solid 1, bis- (the 2- tosyl base oxethyl) ethane (yield 89.2%) of 2-.
Bis- (the 2- tosyl base oxethyl) ethane (0.5mmol) of 213mg 1,2- are taken to be dissolved in 6.25mL N, N- dimethyl
In formamide, add 81mg sodium azide (1.25mmol), controls reaction temperature at 92.5 DEG C, be stirred to react 5 hours, later room temperature
Reaction 19.5 hours；10mL deionized water is added, is extracted with 50mL ethyl acetate, organic phase, organic phase salt water are collected
(50g/L) washing, is dried, filtered with 50mg anhydrous sodium sulfate；Rotary evaporation removes organic solvent, obtained solid by silica gel chromatography
Column purification (eluent is petrol ether/ethyl acetate, V/V=1:2) obtains product 1, bis- (the 2- nitrine ethyoxyl) ethane yields of 2-
For (76.0%).
3) 23mg 1 is taken, bis- (the 2- nitrine base oxethyl) ethane (0.115mmol) of 2- are dissolved in 2mL tetrahydrofuran, are added
89mg1- pyrene formic acid -1- propynyl ester (0.316mmol) stirs 30 minutes, 0.4mL Salzburg vitriol solution is then added dropwise
(18mM) and 0.4mL sodium ascorbate solution (46.8mM) reacts 22 hours at room temperature；Rotary evaporation removes tetrahydrofuran
Afterwards, add 20mL deionized water, extracted with 100mL ethyl acetate, collect organic phase, organic phase is washed with salt water (50g/L)
It washs, dries, filters；Rotary evaporation removing organic solvent, obtained solid by silica gel chromatography column purification (eluent are as follows: methylene chloride/
Methanol, V/V=9:1), obtain solid (((ethane -1,2- diyl is bis- (oxygroup)) are bis- (ethane -2,1- diyl)) it is bis- (1H-1,2,
3- triazole -1,4- diyl)) bis- (methylene) bis- (pyrene -1- carboxylic acid) (yield 88%).
The intermediate of fluorescence probe and final fluorescence probe characterization result in embodiment 1 the result is that identical.
Embodiment 3: the preparation process flow 3 of fluorescence probe
1) it takes 232.5mg 1- pyrene formic acid (0.938mmol) to be dissolved in 2.4mL n,N-Dimethylformamide, 276mg is added
3- propargyl bromide (2.35mmol) and 472mg potassium carbonate (3.28mmol) control reaction temperature at 105 DEG C, are stirred to react 7 hours；
It is cooled to room temperature, adds 25mL deionized water, extracted with 125mL ethyl acetate, collect organic phase, organic phase salt water
(50g/L) washing, is dried, filtered with 125mg anhydrous sodium sulfate；Rotary evaporation removes organic solvent, and obtained solid is through layer of silica gel
Analysis column purification (eluent are as follows: petroleum ether/methylene chloride, V/V=4:1) obtains white solid 1- pyrene formic acid -1- propynyl ester (yield
For 93.5%).
2) 542.5mg triethylene glycol (3.62mmol) dry 3 hours in 120 DEG C of baking ovens are taken, 72mL methylene chloride is dissolved in
In, 1.9g 4-dimethylaminopyridine (15.2mmol) and 978 μ L triethylamines (7.24mmol) are added, are added under condition of ice bath
3.53g p-methyl benzene sulfonic chloride (18.1mmol) stirs 1.5 hours, removes ice bath, reacts 8 hours at room temperature；It is added
18.7mL deionized water, is extracted, and collects organic phase, organic phase is washed with salt water (50g/L), and the anhydrous sulphur of 125mg is added
Sour sodium dries, filters, and rotary evaporation removes organic solvent, obtained solid by silica gel chromatography column purification (eluent are as follows: dichloromethane
Alkane/methanol, V/V=9:1), obtain solid 1, bis- (the 2- tosyl base oxethyl) ethane (yield 89.4%) of 2-.
Bis- (the 2- tosyl base oxethyl) ethane (1.25mmol) of 532mg 1,2- are taken to be dissolved in 18.7mL N, N- dimethyl
In formamide, add 242mg sodium azide (3.75mmol), controls reaction temperature at 105 DEG C, be stirred to react 6 hours, later room temperature
Reaction 24 hours；25mL deionized water is added, is extracted with 125mL ethyl acetate, organic phase, organic phase salt water are collected
(50g/L) washing, is dried, filtered with 125mg anhydrous sodium sulfate；Rotary evaporation removes organic solvent, and obtained solid is through layer of silica gel
It analyses column purification (eluent is petrol ether/ethyl acetate, V/V=1:2), obtains product 1, bis- (the 2- nitrine ethyoxyl) ethane of 2-
(yield 77.8%).
3) 28mg 1 is taken, bis- (the 2- nitrine base oxethyl) ethane (0.14mmol) of 2- are dissolved in 3.5mL tetrahydrofuran, are added
119mg 1- pyrene formic acid -1- propynyl ester (0.42mmol) stirs 30 minutes, 0.4mL Salzburg vitriol solution is then added dropwise
(15.9mM) and 0.4mL sodium ascorbate solution (50.9mM) reacts 24 hours at room temperature；Rotary evaporation removes tetrahydrofuran
Afterwards, add 25mL deionized water, extracted with 125mL ethyl acetate, collect organic phase, organic phase is washed with salt water (50g/L)
It washs, dries, filters；Rotary evaporation removing organic solvent, obtained solid by silica gel chromatography column purification (eluent are as follows: methylene chloride/
Methanol, V/V=9:1), obtain solid (((ethane -1,2- diyl is bis- (oxygroup)) are bis- (ethane -2,1- diyl)) it is bis- (1H-1,2,
3- triazole -1,4- diyl)) bis- (methylene) bis- (pyrene -1- carboxylic acid) (yield 89.5%).
The intermediate of fluorescence probe and final fluorescence probe characterization result in embodiment 1 the result is that identical.
Embodiment 4: the preparation of fluorescence probe dispersion liquid
Taking 0.8mg solid probe compound, (((ethane -1,2- diyl is bis- (oxygroup)) are bis- (ethane -2,1- diyl)) are double
(1H-1,2,3- triazoles-Isosorbide-5-Nitrae-diyl)) bis- (methylene) bis- (pyrene -1- carboxylic acids) be dissolved in 1mL dimethyl sulfoxide, fluorescence is made
Probe dispersion liquid (1mM).
Embodiment 5: the photoluminescent property of fluorescence probe
The structure for the fluorescence probe that the present invention synthesizes is the symmetrical structure of two pyrene units and triazole being connected by triethylene glycol,
Two of them pyrene ring is fluorophor, and two triazoles and oxygen atom are recognition group；Two pyrene rings are formed sharp by pi-pi accumulation
Base associated matter, under 345nm exciting light, fluorescence probe generates a weaker blue-fluorescence at 420nm, in 515nm or so
There is the yellow-green fluorescence of a stronger excimer at place.After silver ion is added, recognition group (triazole) and silver ion network
Conjunction forms structure as shown in Figure 4, increases the distance of two pyrene units, and the amount of excimer is reduced, and excimer exists
Fluorescent emission intensity at 515nm also accordingly weakens；And the quantity of pyrene monomer increases, the fluorescence intensity at corresponding 420nm
(as shown in Figure 5) is gradually increased, and realizes ratio test (as shown in Figure 6).Therefore, by means of the irradiation of ultraviolet lamp (365nm),
In the presence of silver ion, the fluorescence that system can be observed becomes blue (as shown in Figure 7) from yellow green；When trivalent is added in system
After chromium ion, recognition group (triazole and oxygen atom) forms complex compound as shown in Figure 4 in conjunction with trivalent chromic ion, and system exists
Under 345nm exciting light, intramolecular energy occurs, so that in the energy transfer to trivalent chromic ion of the excimer of pyrene,
Fluorescence (as shown in Figure 5) of the excimer at 515nm has been quenched；Under the irradiation of ultraviolet lamp (365nm), system it is yellowish green
Color fluorescent weakening (as shown in Figure 7).Therefore, fluorescence probe according to the present invention can be formed with silver ion and trivalent chromic ion
Different complex compounds can realize the Ratio-type fluorescence inspection to silver ion and trivalent chromic ion by different interactions respectively
It surveys (as shown in Figure 6),
Embodiment 6: fluorescence detection of the fluorescence probe to silver ion and trivalent chromic ion in water
With the fluorescence probe (preparation of embodiment 1) of synthesis to the metal ion in Tris buffer (10mM, pH 7.0) into
Row fluorimetric analysis.It is 0.02mM that fluorescence probe, which is made into mother liquid concentration with dimethyl sulfoxide, metal ion (calcium ion, aluminium from
Son, divalent manganesetion, ferric ion, potassium ion, cobalt ions, magnesium ion, barium ions, silver ion, zinc ion, trivalent chromium from
Son, nickel ion, copper ion, mercury ion, cadmium ion) to be made into mother liquid concentration with water be 10mM；Fluorescence probe is diluted to when test
Ultimate density is 1 μM, concentration of metal ions 0.1mM.Concrete operations are as follows: take 50 μ L probe dispersion liquids, 10 μ L metal ions are molten
Liquid is added in 940 μ L Tris buffers, is configured to 1mL solution to be measured, is stirred 2 hours on shaking table, survey respectively its
Fluorescent emission intensity under 345nm wavelength excitation, as a result as shown in Figure 5.
Embodiment 7: hand-held ultraviolet lamp irradiation under (365nm), naked eyes resolved fluorometric probe in water silver ion and
The different responses of trivalent chromic ion.
The probe prepared in embodiment 1 with dimethyl sulfoxide be made into mother liquid concentration be 0.02mM, silver ion and trivalent chromium from
It is 10mM that son, which is made into mother liquid concentration with water,；When test by probe dilution at ultimate density be 1 μM, concentration of metal ions 0.1mM.
Concrete operations are as follows: take 25 μ L probe dispersion liquids, 5 μ L metal ion solutions are added in 470 μ L Tris buffers, are configured to
0.5mL solution to be measured stirs 2 hours on shaking table, observes it under hand-held ultraviolet lamp irradiation (365nm), test fluid color
Variation.
As seen from the above-described embodiment, fluorescence probe prepared by the present invention can be used for simultaneously to silver ion and trivalent chromic ion
Ratio-type fluorescence detection, this mode can greatly reduce the influence of external factor compared with single fluorescence enhancement or decrease,
Improve detection accuracy and accuracy；In addition, probe can be realized under hand-held ultraviolet lamp irradiation naked eyes differentiate to silver ion and
The different responses of trivalent chromic ion.Detection architecture of the invention is easy to use, quick, easy to promote and utilize, and the present invention synthesizes
Fluorescence probe can detect silver ion and trivalent chromic ion simultaneously, more traditional only detection silver ion or only detect trivalent chromic ion
Detection method it is time saving and energy saving, be expected to be used for the quantitative analysis of silver ion and trivalent chromic ion in the samples such as chemistry, environment.
Claims (10)
1. the Ratiometric fluorescent probe that one kind can be used for silver ion and trivalent chromic ion detection simultaneously, which is characterized in that the fluorescence
Probe is (((ethane -1,2- diyl is bis- (oxygroup)) are bis- (ethane -2,1- diyl)) are bis- (1H-1,2,3- triazole -1,4- diyl))
Bis- (methylene) is bis- (pyrene -1- carboxylic acid), and structural formula is as follows:
2. preparing the Ratiometric fluorescent probe that one kind described in claim 1 can be used for silver ion and trivalent chromic ion detection simultaneously
Method, which is characterized in that comprise the steps of:
1) bis- (the 2- nitrine base oxethyl) ethane of 1- pyrene formic acid -1- propynyl ester and 1,2- are dissolved in tetrahydrofuran；
2) Salzburg vitriol is added into step 1) acquired solution and ascorbic acid sodium water solution, reaction temperature is room temperature, instead
It answers 20-24 hours；
3) it after rotary evaporation removes tetrahydrofuran, is extracted with ethyl acetate/deionized water, organic phase is collected, by organic phase
It is washed with brine, dries, filters；Rotary evaporation removes organic solvent, and it is glimmering to obtain solid for obtained solid by silica gel chromatography column purification
Light probe, i.e. (((ethane -1,2- diyl is bis- (oxygroup)) are bis- (ethane -2,1- diyl)) bis- (1H-1,2,3- triazoles-Isosorbide-5-Nitraes-two
Base)) bis- (methylene) bis- (pyrene -1- carboxylic acid).
3. preparation method according to claim 2, which is characterized in that the system of step 1) the 1- pyrene formic acid -1- propynyl ester
Preparation Method is as follows: 1- pyrene formic acid being dissolved in n,N-Dimethylformamide, 3- propargyl bromide and potassium carbonate is added, controls reaction temperature
At 80-105 DEG C, it is stirred to react 5-7 hours；It is cooled to room temperature, deionized water is added, is then extracted with ethyl acetate；It receives
Collect organic phase, organic phase is washed with brine, is dried, filtered with anhydrous sodium sulfate；Rotary evaporation removes organic solvent, and gained is solid
Body by silica gel chromatography column purification obtains solid 1- pyrene formic acid -1- propynyl ester.
4. preparation method according to claim 3, which is characterized in that the molar ratio of the 1- pyrene formic acid and 3- propargyl bromide is
1:1.5-1:2.5；The molar ratio of the 1- pyrene formic acid and potassium carbonate is 1:(1.5-3.5)；N, N- is added in every mmol 1- pyrene formic acid
Dimethylformamide 1-2.5mL.
5. preparation method according to claim 2, which is characterized in that step 1) 1, the 2- bis- (2- nitrine base oxethyls)
Ethane the preparation method is as follows: by triethylene glycol put in a vacuum drying oven 95-120 DEG C it is 2-3 hours dry, be then dissolved in dichloromethane
In alkane, triethylamine and 4-dimethylaminopyridine is added, p-methyl benzene sulfonic chloride is added under condition of ice bath, stirring 0.5-1.5 is small
When, ice bath is removed, the reaction was continued at room temperature 3-8 hours；Deionized water is added, is extracted, organic phase is collected, by organic phase
It is washed with brine, is dried, filtered with anhydrous sodium sulfate, rotary evaporation removes organic solvent, and obtained solid by silica gel chromatography column is pure
Change, obtains solid 1, bis- (the 2- tolysulfonyl base oxethyl) ethane of 2-；By bis- (the 2- tolysulfonyl base oxethyl) second of 1,2-
Alkane is dissolved in n,N-Dimethylformamide, and sodium azide is added, and is controlled reaction temperature at 80-105 DEG C, is stirred to react 4-6 hours,
It normal-temperature reaction 15-24 hours later, adds deionized water and then is extracted with ethyl acetate；Organic phase is collected, it will be organic
It is mutually washed with brine, is dried, filtered with anhydrous sodium sulfate；Rotary evaporation removes organic solvent, obtained solid by silica gel chromatography column
Purifying, obtains solid 1, bis- (the 2- nitrine base oxethyl) ethane of 2-.
6. preparation method according to claim 5, which is characterized in that methylene chloride 15-20mL is added in every mmol triethylene glycol；
The molar ratio of the triethylene glycol and triethylamine is 1:1-1:1.2；The molar ratio of the triethylene glycol and 4-dimethylaminopyridine is
1:3-1:4.2；The molar ratio of the triethylene glycol and p-methyl benzene sulfonic chloride is 1:2.8-1:5；Every bis- (2- toluene of mmol 1,2-
Sulphonyl base oxethyl) ethane addition N,N-dimethylformamide 10-15mL；The 1,2- is bis- (2- tolysulfonyl base oxethyl)
The molar ratio of ethane and sodium azide is 1:2-1:3.
7. preparation method according to claim 2, which is characterized in that in step 1), bis- (the 2- azidos of every mmol 1,2-
Ethyoxyl) ethane addition tetrahydrofuran 10-25mL；Bis- (the 2- nitrine base oxethyl) ethane of 1,2- and 1- pyrene formic acid -1- third
The molar ratio of alkynes ester is 1:2.5-1:3.
8. preparation method according to claim 2, which is characterized in that the step 2) Salzburg vitriol and ascorbic acid
The molar ratio of sodium is 1:2-1:3.2；The molar ratio of the Salzburg vitriol and bis- (the 2- nitrine base oxethyl) ethane of 1,2- is
1:10-1:22。
9. preparation method according to claim 2, which is characterized in that drying described in step 3) is carried out with anhydrous sodium sulfate
It is dry；The salt water is the sodium chloride solution that mass percentage concentration is 5%-10%.
10. Ratiometric fluorescent probe described in claim 1 is applied to while identifying in the detection of silver ion and trivalent chromic ion.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676158A (en) * | 2012-05-16 | 2012-09-19 | 陕西师范大学 | Pyrene-contained bis-imidazole type fluorescence probe as well as synthetic method and application thereof |
| CN103275697A (en) * | 2013-05-28 | 2013-09-04 | 陕西师范大学 | Di-pyrene amphiphilic fluorescent probe and synthesis method and application thereof |
| CN104592983A (en) * | 2014-11-28 | 2015-05-06 | 渤海大学 | Fluorescent probes based on pyrene, and preparation method and application thereof |
| CN104610228A (en) * | 2015-01-21 | 2015-05-13 | 济南大学 | Trivalent chromic ion fluorescence probe compound as well as preparation and application thereof |
| KR101657040B1 (en) * | 2015-05-27 | 2016-09-19 | 충남대학교산학협력단 | Nanofibril conjugate for detection of metal ion and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676158A (en) * | 2012-05-16 | 2012-09-19 | 陕西师范大学 | Pyrene-contained bis-imidazole type fluorescence probe as well as synthetic method and application thereof |
| CN103275697A (en) * | 2013-05-28 | 2013-09-04 | 陕西师范大学 | Di-pyrene amphiphilic fluorescent probe and synthesis method and application thereof |
| CN104592983A (en) * | 2014-11-28 | 2015-05-06 | 渤海大学 | Fluorescent probes based on pyrene, and preparation method and application thereof |
| CN104610228A (en) * | 2015-01-21 | 2015-05-13 | 济南大学 | Trivalent chromic ion fluorescence probe compound as well as preparation and application thereof |
| KR101657040B1 (en) * | 2015-05-27 | 2016-09-19 | 충남대학교산학협력단 | Nanofibril conjugate for detection of metal ion and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Dual-mode recognition of transition metal ions by bis-triazoles chained pyrenes;Hao-Chih Hung，et al;《Tetrahedron Letters》;20081105;第50卷;第302-305页 |
| Hsuan-Fu Wang，et al.Highly selective fluorescent sensors for mercury(II) ions and their applications in living cell imaging.《Tetrahedron》.2013,第69卷第1965-1969页. |
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