CN107247042B - Symmetry is copolymerized 5 aromatic hydrocarbons indirect fluorescence detection mercury ion of column and iodide ion method - Google Patents

Symmetry is copolymerized 5 aromatic hydrocarbons indirect fluorescence detection mercury ion of column and iodide ion method Download PDF

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CN107247042B
CN107247042B CN201710454120.2A CN201710454120A CN107247042B CN 107247042 B CN107247042 B CN 107247042B CN 201710454120 A CN201710454120 A CN 201710454120A CN 107247042 B CN107247042 B CN 107247042B
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CN107247042A (en
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魏太保
陈进发
韩冰冰
张有明
林奇
姚虹
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Heze Smart New Material Technology Co ltd
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432Quenching

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Abstract

The method that the present invention relates to the use of symmetry copolymerization 5 aromatic hydrocarbons indirect of column identification mercury ion and iodide ion, belongs to cation detection technical field.5 benzene ring units that symmetry is copolymerized 5 aromatic hydrocarbons of column provide a good fluorescence signal group, bromine atom easily occurs nucleophilic substitution with iodide ion and generates new compound (DBP5I), and the compound containing iodine easily with mercury ion ligand complex, to make the fluorescent quenching of DBP5I.Therefore, using this property, mercury ion and iodide ion can be identified indirectly.

Description

Symmetry is copolymerized 5 aromatic hydrocarbons indirect fluorescence detection mercury ion of column and iodide ion method
Technical field
The present invention relates to a kind of methods with symmetry copolymerization 5 aromatic hydrocarbons indirect of column identification mercury ion and iodide ion, belong to Cation detection technical field.
Background technique
Mercury is largely applied in industrial chemicals, electrical equipment, silver amalgam and battery at present, in its natural state Mercury and the oxide of mercury have very big harmfulness to human body and natural environment.In order to detect and monitor various feelings A kind of mercury under condition, it is necessary to effective method.In the method for various detection mercury ions, fluorescence probe method has highly sensitive Degree, maneuverable feature, have had been to be concerned by more and more people.Up to the present, the fluorescence probe of many mercury ions has been Through being synthesized, but most sensor all contains sulphur atom, sulphur atom and mercury Hg-S key easy to form, and to identify Process is irreversible, it is difficult to recycle.And the sensor of most of sulfur-bearing is all highly susceptible to interfere and influence in sulfur-rich environment, It is difficult to play the effect of detection mercury ion.Therefore a kind of fluorescent optical sensor without element sulphur is just needed to be used to detect mercury ion.
Iodine is one of the important element of synthesized human thyroid hormone, and the absorption surplus for lacking iodine and iodine can all influence body Normal function, or even bring major disease, such as the abnormal development of brain, physique is short and small, physical efficiency is insufficient and metabolic disorder. Therefore, the detection of the content of iodine in environment and food is also very necessary.Since iodide ion own charge density is loose and Itself ionic radius is bigger than normal, therefore iodide ion sensor annoyings many researchers all the time.However, iodide ion easily occurs Therefore nucleophilic substitution can use its this characteristic to detect iodide ion.
Macrocyclic host compound of the column aromatic hydrocarbons as a new generation.It has been shown in terms of host-guest chemistry very outstanding Effect.Due to containing multiple phenyl ring, outstanding fluorescence radiation performance is shown.By the modification to column aromatic hydrocarbons structure, perhaps The fluorescence chemical sensor of multifunction is developed well.
Summary of the invention
The purpose of the present invention is the properties according to column aromatic hydrocarbons, provide a kind of glimmering using symmetry copolymerization 5 aromatic hydrocarbons indirect of column The method of light detection mercury ion and iodide ion.
One, the structure of symmetry copolymerization 5 aromatic hydrocarbons of column
Symmetry is copolymerized 5 aromatic hydrocarbons of column, is labeled as DBP5.5 benzene ring units that symmetry is copolymerized 5 aromatic hydrocarbons of column provide one very Good fluorescence signal group, bromine atom easily occurs nucleophilic substitution with iodide ion and generates new compound (DBP5I), and contains iodine Compound easily with mercury ion ligand complex, to make the fluorescent quenching of DBP5I.It therefore, can be indirectly using this property Identify mercury ion and iodide ion.The structural formula of symmetry column aromatic hydrocarbons is as follows:
Two, the fluorescence identifying performance of symmetry copolymerization 5 aromatic hydrocarbons of column
1, to cationic fluorescent recognition performance
The dimethyl sulphoxide solution (2 × 10 of 0.5mL DBP5 is pipetted respectively-3 mol·L-1) and 0.5mL IDimethyl Sulfoxide solution (5 × 10-3 mol·L-1) in a series of 10 mL colorimetric cylinders, and by the mixed solution labeled as DBP5I solution. Then Fe is added in the solution respectively3+, Hg2+, Ca2+, Co2+, Ni2+, Cd2+, Pb2+, Zn2+, Cr3+, Mg2+, Ag+Dimethyl Sulfoxide solution (5 × 10-4 mol·L-1) 0.5 mL, add distilled water 0.5mL, then be diluted to 5mL with dimethyl sulfoxide, at this time The concentration of DBP5I is 2 × 10-4mol·L-1, cation concn is 0.25 times of DBP5I concentration.It places 1 minute after mixing Response of the receptor to each cation is observed in left and right.
It was found that in DBP5I solution, after being separately added into above-mentioned cationic solution, in corresponding ultraviolet spectra, There is absorption peak at 295nm.In its corresponding fluorescence emission spectrum, Hg2+Addition so that emission peak of the DBP5I at 328nm is disappeared It loses (Fig. 1), and the addition of remaining cation has no significant effect the fluorescence spectrum of DBP5I solution.Correspondingly, Hg2+Addition make The fluorescent quenching of DBP5I solution, and the addition of remaining cation does not influence the fluorescence of DBP5I solution.
2, the titration experiments of symmetry copolymerization column 5 aromatic hydrocarbons and mercury ion
Pipette the DMSO (aqueous 10%) solution (2.0 × 10 of 2.0mL DBP5I-4Mol/L) in quartz cell, added with accumulation Sample method is gradually added into Hg2+ Dimethyl sulphoxide solution, its fluorescence emission spectrum (Fig. 2) is surveyed in 25 DEG C.Titration experiments explanation, The fluorescence intensity of DBP5I is by Hg2+The influence of concentration weakens along with the increase of iron concentration.And it is real according to titration Test to have obtained DBP5I to Hg2+The detection of fluorescence spectrum be limited to 3.73 × 10−8mol/L.Thus illustrate, DBP5I can single choosing Selecting property fluorescence identifying mercury ion, and it is very high to the detection sensitivity of mercury ion, and therefore, DBP5 detects mercury ion side in indirect There is potential application value in face.
Fig. 3 is the Hg of various concentration2+The fitting a straight line figure of DBP5I in the presence of (0 ~ 0.08 times).Fitting a straight line figure can be clear The fluorescence intensity of clear clear reflection DBP5I is in 0 ~ 0.08 times of Hg2+Variation tendency in concentration range.Pass through fitting a straight line figure It can be found that Hg2+In 0 ~ 0.08 times of equivalent, Hg2+Fluorescence intensity with DBP5I is in following linear relationship:
Y=- 2205.4269X+311, R2=0.9936
Y --- symmetry is copolymerized 5 aromatic hydrocarbons+I of column-Fluorescence intensity: unit: a.u.
X——Hg2+Relative concentration, unit: mol/L.
3, the cationic interference free performance detection of symmetry copolymerization 5 aromatic hydrocarbons of column
In order to measure DBP5I to Hg2+Detection effect, we have carried out following test again: taking two groups of 10ml colorimetric cylinders point It Jia Ru not 0.5mL DBP5 solution and 0.5mL ISolution, then be separately added into the various cations of 0.5mL dimethyl sulfoxide it is molten Liquid (4 × 10-3mol·L−1), add distilled water 0.5mL, is then diluted to 5mL scale with dimethyl sulfoxide.Divide again in another set Not plus 0.5mL Hg2+, 0.5mL Fe is separately added into each colorimetric cylinder3+, Ca2+, Co2+, Ni2+, Cd2+, Pb2+, Zn2+, Cr3 +, Mg2+, Ag+Dimethyl sulphoxide solution (5 × 10-4 mol·L-1), add distilled water 0.5mL, is then diluted with dimethyl sulfoxide To 5mL scale.Above-mentioned solution is observed after mixing.
For above-mentioned solution left standstill after 1 minute, 25 DEG C are surveyed its fluorescence emission spectrum.As a result, it has been found that above-mentioned ten kinds of cations are added Afterwards, DBP5I fluorescent quenching at 328nm, this and Hg2+Influence to DBP5I is consistent.To illustrate such DBP5 compound Detection Hg indirectly2+Not by the interference (see figure 4) of other cations.
Experiment shows in the aqueous DMSO solution of symmetry copolymerization 5 aromatic hydrocarbons of column that the percentage by volume of water is 5 ~ 15%, symmetrically Property copolymerization 5 aromatic hydrocarbons of column concentration be 1 × 10-4~4×10-4mol·L-1, symmetry copolymerization 5 aromatic hydrocarbons+I of columnIt can be highly sensitive single One Selective recognition Hg2+, and Hg2+Concentration and BTAP5 fluorescence intensity be in above-mentioned linear relationship.
4、DBP5+Hg2+Research to Anion Recognition performance
The DMSO solution (2 × 10 of 0.5 mL DBP5 is pipetted respectively-3 mol·L-1) in a series of 10 mL colorimetric cylinders, It is separately added into 0.5 mL Hg2+DMSO solution (2 × 10-3 mol·L-1) form mixed system DBP5+Hg2+, then distinguish again F is added, Cl, Br, I, AcO, H2PO4 , HSO4 , ClO4 , CN、NO3 DMSO solution (4 × 10-3 mol·L-1) 0.5 ML adds distilled water 0.5mL, then is diluted to 5mL with DMSO.Receptor DBP5+Hg at this time2+Concentration is 2 × 10-4mol·L-1, yin from Sub- concentration is 2 times of acceptor density.Observe receptor DBP5+Hg2+Response to each anion.
As a result, it has been found that in fluorescence spectrum, only IAddition so that DBP5+Hg2+Fluorescent quenching of the solution at 328nm (λ ex=295nm), and the addition of other anion, DBP5+Hg2+The fluorescence spectrum of solution does not have any apparent variation (Fig. 5), Illustrate DBP5+Hg2+To IShow very strong single-minded selectivity, therefore fluorescence identifying I that can be highly selective, highly sensitive
5、DBP5+Hg2+With ITitration experiments
Pipette 2.0mL DBP5+Hg2+Solution (2.0 × 10-4Mol/L it) in quartz cell, is gradually added into accumulation sample-adding method IDimethyl sulphoxide solution, its fluorescence emission spectrum (Fig. 6) is surveyed in 25 DEG C.Titration experiments explanation, DBP5+Hg2+Fluorescence it is strong Degree is by IThe influence of concentration increases along with the increase of iodide ion concentration.And DBP5+Hg has been obtained according to titration experiments2 +To IThe detection of fluorescence spectrum be limited to 3.51 × 10−7mol/L.Thus illustrate, DBP5+Hg2+It can single selective fluorescence identifying Iodide ion, and it is very high to the detection sensitivity of iodide ion, therefore, DBP5+Hg2+There is potential application in iodide ion context of detection Value.
Fig. 7 is the I of various concentrationDBP5+Hg in the presence of (0 ~ 1.2 times)2+Fitting a straight line figure.Fitting a straight line figure can be clear Clear clear reflection DBP5+Hg2+Fluorescence intensity in 0 ~ 1.2 times of IVariation tendency in concentration range.Pass through fitting a straight line figure It can be found that IIn 0 ~ 1.2 times of equivalent and DBP5+Hg2+Fluorescence intensity be in preferable linear relationship:
Y=- 168.068X+321.191, R2=0.9950
Y——DBP5+Hg2+Fluorescence intensity: unit: a.u.
X——IRelative concentration, unit: mol/L.
6、DBP5+Hg2+Anion interference free performance detection
In order to measure DBP5+Hg2+To IDetection effect, we have carried out following test again: taking two groups of 10ml colorimetric cylinders It is separately added into the 0.5mL DBP5+Hg2+Solution, then be separately added into the various anion of 0.5mL dimethyl sulphoxide solution (4.0 × 10-3mol·L−1), add distilled water 0.5mL, is then diluted to 5mL scale with dimethyl sulfoxide.Add respectively again in another set 0.5mL I, 0.5mL F is separately added into each colorimetric cylinder, Cl, Br, AcO, H2PO4 , HSO4 , ClO4 , CN, NO3 Dimethyl sulphoxide solution (4.0 × 10-3 mol·L-1), add distilled water 0.5mL, is then diluted to 5mL with dimethyl sulfoxide and carves Degree.Above-mentioned solution is observed after mixing.
Above-mentioned solution left standstill surveys its fluorescence emission spectrum after 1 minute, in 25 DEG C.As a result, it has been found that be added above-mentioned nine kinds of yin from After son, DBP5+Hg2+The fluorescent quenching at 328nm, this and ITo DBP5+Hg2+Influence be consistent.To illustrate such DBP5+Hg2+Compound test INot by the interference (see figure 8) of other anion.
Experiment shows in the aqueous DMSO solution of symmetry copolymerization 5 aromatic hydrocarbons of column that the percentage by volume of water is 5 ~ 15%, symmetrically Property copolymerization 5 aromatic hydrocarbons of column concentration be 1 × 10-4~4×10-4mol·L-1, symmetry copolymerization 5 aromatic hydrocarbons+I of columnIt can be highly sensitive single One Selective recognition I, and IConcentration and BTAP5+ Hg2+Fluorescence intensity be in above-mentioned linear relationship.
Detailed description of the invention
Fig. 1 is DBP5I(DBP5+I) and fluorescence spectrum (excitation wavelength: 295nm, hair when being added 11 kinds of cation The long 328nm of ejected wave).
Fig. 2 is the Hg of various concentration2+The fluorescence spectrum of DBP5I in the presence of (0 ~ 0.4 times).
Fig. 3 is the Hg of various concentration2+The fitting a straight line figure of DBP5I in the presence of (0 ~ 0.08 times).
Fig. 4 is the interference free performance that DBP5I identifies mercury ion;1 ~ 22 respectively represents DBP5I, Hg2+、Fe3+、Ca2+、Co2 +、Ni2+、Cd2+、Pb2+、Zn2+、Cr3+、Mg2+And Ag+
Fig. 5 is DBP5+Hg2+And its fluorescence spectrum (excitation wavelength: 295nm, transmitted wave when being added 2 times of anion It is long: 328nm).
Fig. 6 is the I of various concentrationReceptor DBP5+Hg in the presence of (0 ~ 2.4 times)2+Fluorescence spectrum.
Fig. 7 is the I of various concentrationDBP5+Hg in the presence of (0 ~ 1.2 times)2+Fitting a straight line figure.
Fig. 8 is DBP5+Hg2+To the interference free performance of iodide ion identification;1 ~ 20 respectively represents DBP5, DBP5+Hg2++I、F、Cl、Br、AcO、H2PO4 、HSO4 、ClO4 、CN、NO3
Specific embodiment
Hg is detected to symmetry of the present invention copolymerization 5 aromatic hydrocarbons of column (DBP5) indirect below by specific embodiment2+、ISide Method is described further.
Embodiment 1, detection Hg2+
Pipette the DMSO solution (2 × 10 of DBP5-3 mol·L-1) in a series of 10 mL colorimetric cylinders, first it is separately added into I DMSO solution (5 × 10-3 mol·L-1);It is separately added into Fe again3+, Hg2+, Ca2+, Co2+, Ni2+, Cd2+, Pb2+, Zn2+, Cr3+, Mg2+, Ag+Dimethyl sulphoxide solution (5 × 10-4 mol·L-1), if the fluorescent quenching of solution, that illustrate to be added is Hg2+, If what the fluorescence of solution there is no variation, illustrated to be added is other cations.
Embodiment 2,
Detect IIon
Pipette the DMSO solution (2 × 10 of DBP5-3 mol·L-1) in a series of 10 mL colorimetric cylinders, first it is separately added into Hg2+DMSO solution (2 × 10-3 mol·L-1);It is separately added into F thereto again, Cl, Br, I, AcO, H2PO4 , HSO4 , ClO4 , CN、NO3 Solution (4 × 10-3 mol·L-1), if the fluorescent quenching of solution, that illustrate to be added is I;If solution Fluorescence does not change, then illustrate to be added is other anion.

Claims (10)

1. with the method for symmetry copolymerization 5 aromatic hydrocarbons indirect fluorescence detection mercury ion of column, it is characterised in that: in a series of symmetry It is copolymerized in the aqueous DMSO solution of 5 aromatic hydrocarbons of column, I is first added;It is separately added into cationic Fe again3+, Hg2+, Ca2+, Co2+, Ni2+, Cd2 +, Pb2+, Zn2+, Cr3+, Mg2+, Ag+Dimethyl sulphoxide solution, if the fluorescent quenching of solution, illustrate be added be mercury ion, If what the fluorescence of solution there is no variation, illustrated to be added is other cations;
The structural formula of symmetry copolymerization 5 aromatic hydrocarbons of column is as follows:
2. the method for being copolymerized 5 aromatic hydrocarbons indirect fluorescence detection mercury ion of column with symmetry as described in claim 1, feature exist In: IAdditional amount be that symmetry is copolymerized 2 ~ 3 times of 5 aromatic hydrocarbons mole of column.
3. as claimed in claim 1 or 2 with the method for symmetry copolymerization 5 aromatic hydrocarbons indirect fluorescence detection mercury ion of column, feature Be: symmetry is copolymerized in the aqueous DMSO solution of 5 aromatic hydrocarbons of column, and the concentration that symmetry is copolymerized 5 aromatic hydrocarbons of column is 1 × 10-4~4×10-4mol·L-1
4. as claimed in claim 1 or 2 with the method for symmetry copolymerization 5 aromatic hydrocarbons indirect fluorescence detection mercury ion of column, feature It is: Hg2+5 aromatic hydrocarbons+I of column is copolymerized with symmetryFluorescence intensity be in following linear relationship:
Y=- 2205.4269X+311, R2=0.9936
Y --- symmetry is copolymerized 5 aromatic hydrocarbons+I of column-Fluorescence intensity: unit: a.u.
X——Hg2+Relative concentration, unit: mol/L.
5. the method for being copolymerized 5 aromatic hydrocarbons indirect fluorescence detection mercury ion of column with symmetry as described in claim 1, feature exist In: symmetry is copolymerized in the aqueous DMSO solution of 5 aromatic hydrocarbons of column, and the percentage by volume of water is 5 ~ 15%.
6. with the method for symmetry copolymerization 5 aromatic hydrocarbons indirect fluorescence detection iodide ion of column, it is characterised in that: in a series of symmetry It is copolymerized the aqueous DMSO solution of 5 aromatic hydrocarbons of column, is first separately added into Hg2+;It is separately added into F thereto again, Cl, Br, I, AcO, H2PO4 , HSO4 , ClO4 , CN, NO3 Solution, if the fluorescent quenching of solution, that illustrate to be added is I;If the fluorescence of solution is not It changes, then illustrate to be added is other anion;The structural formula of symmetry copolymerization 5 aromatic hydrocarbons of column is as follows:
7. the method for being copolymerized 5 aromatic hydrocarbons indirect fluorescence detection iodide ion of column with symmetry as claimed in claim 6, feature exist In: Hg2+Additional amount be that symmetry is copolymerized 1 ~ 2 times of 5 aromatic hydrocarbons mole of column.
8. as claimed in claims 6 or 7 with the method for symmetry copolymerization 5 aromatic hydrocarbons indirect fluorescence detection iodide ion of column, feature Be: symmetry is copolymerized in the aqueous DMSO solution of 5 aromatic hydrocarbons of column, and the concentration that symmetry is copolymerized 5 aromatic hydrocarbons of column is 1 × 10-4~4×10-4 mol·L-1
9. as claimed in claims 6 or 7 with the method for symmetry copolymerization 5 aromatic hydrocarbons indirect fluorescence detection iodide ion of column, feature It is: I5 aromatic hydrocarbons+Hg of column is copolymerized with symmetry2+Fluorescence intensity be in following linear relationship:
Y=- 168.068X+321.191, R2=0.9950
Y——DBP5+Hg2+Fluorescence intensity: unit: a.u.
X——IRelative concentration, unit: mol/L.
10. as claimed in claims 6 or 7 with the method for symmetry copolymerization 5 aromatic hydrocarbons indirect fluorescence detection iodide ion of column, feature Be: symmetry is copolymerized in the aqueous DMSO solution of 5 aromatic hydrocarbons of column, and the percentage by volume of water is 5 ~ 15%.
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