CN107337654A - A kind of fluorescence probe for analyzing mercury ion, preparation method and application - Google Patents
A kind of fluorescence probe for analyzing mercury ion, preparation method and application Download PDFInfo
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- CN107337654A CN107337654A CN201710559067.2A CN201710559067A CN107337654A CN 107337654 A CN107337654 A CN 107337654A CN 201710559067 A CN201710559067 A CN 201710559067A CN 107337654 A CN107337654 A CN 107337654A
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Abstract
The present invention relates to a kind of quick high-selectivity mercury ion fluorescence probe.It is thiocarbonic acid esters compound, and its structural formula is.This kind of probe can be realized at least one in following technique effect：Mercury ion is identified with high selectivity；Quickly mercury ion can be realized and responded；Big Stokes shift；Property is stable, can preserve use for a long time；And there is stronger antijamming capability.
Description
Technical field
The present invention relates to fluorescence probe and preparation method of the thiocarbonic acid esters compound as analysis mercury ion, Neng Gouxun
Speed to the sensitive identification of mercury ion high selectivity, or its can in determination sample mercury ion concentration.
Background technology
Mercury is the glittering heavy liquid of silvery white, and chemical property is stable, and alkali is also insoluble in insoluble in acid.Under mercury normal temperature
The compound of evaporation, mercury vapour and mercury has hypertoxic (chronic) more.Mercury it is widely used, for manufacturing science measuring instrument（Such as temperature
Degree meter etc.）, medicine, electrode, catalyst etc..Mercury generally existing in nature, all contain micro mercury in general animals and plants,
Therefore in our food, with the presence of micro mercury, can be metabolized by excretion, hair etc., it is not unhealthful.
Mercury is the heavy metal contaminants that a kind of bio-toxicity is extremely strong in environment, and it enters after organism it is difficult to be discharged, sternly
Human health is threatened again.Central nervous system, digestive system and kidney are mainly involved in harm of the mercury to human body, are to breathing in addition
System, skin, blood and eyes also have a certain impact.Between the past more than ten years, the concentration of mercury is held in environment in world wide
It is continuous to rise, cause the very big concern of national governments and environmental protection organization, turn into another whole world after climate change problem
Environmental problem.
In consideration of it, the analysis method that effective detection mercury ion is capable of in development is of crucial importance and significant.Nowadays
The analysis method of the detection mercury ion of report includes volumetric analysis, Optical Analysis Method, the chromatography of ions (IC), mercury ion selection
Electrode method, the methods of on-line analysis method.Fluorescence probe turns into due to the advantages of its is peculiar in these numerous detection methods
Researcher's focus of attention.However, the fluorescence probe reported at present still suffers from some problems, including selectivity is not good enough, sound
Answer that speed is not fast enough, synthesis is complicated.Due to other ions in environment such as cadmium ion, lead ion, magnesium ion, aluminium ion, divalence
Other metals such as iron ion, ferric ion, chromium ion, calcium ion, zinc ion, sodium ion, potassium ion, cobalt ions and nickel ion
Ion, the detection that it can be to mercury ion form potential interference, and therefore, development is quick, and high selectivity, high sensitivity, synthesis are simple
Mercury ion fluorescence probe be those skilled in the art be badly in need of solve problem.
The content of the invention
This area is badly in need of one kind and prepares simple quick high-selectivity mercury ion fluorescence probe, so as to effective detection mercury
Ion.And provide it is a kind of synthesize simple preparation method, and high selectivity, high sensitivity, quickly identify mercury ion.
Specifically, the invention provides a kind of fluorescence probe for analysing mercury ion, it is thiocarbonic acid esters compound, its
Structure is as shown in Equation 1：
Formula 1
Wherein：R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15 are hydrogen atom, and carbon atom is
1-3 straight or branched alkyl, carbon atom be 1-3 straight or branched alkoxyl, sulfonic group, ester group, carboxyl；R1, R2, R3,
R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14 and R15 are identical or different.
Preferably, fluorescence probe of the invention, its structural formula are as shown in Equation 2：
Formula 2.
Present invention also offers the preparation method of mercury ion fluorescence probe, it is characterised in that using following steps:
Hexamethylenetetramine shown in formula 4 is dissolved in 20 mL trifluoroacetic acid, adds the p-methyl phenol shown in formula 3, two
Person's mol ratio is 4:1,100 DEG C is heated to reflux 6 hours, and shading treatment, adds product in frozen water after having reacted, and separates out solid
Filtered after body, obtain sterling formula 5
The formula 5 of 3 formula of formula 4
Compound shown in formula 5 is dissolved in absolute ethyl alcohol, adds the amino benzenethiol shown in formula 6, the two mol ratio is 1:
1, stirring at normal temperature, 37% hydrochloric acid and 30% hydrogen peroxide are added dropwise in whipping process, react 30 min, then filtered
Obtain sterling formula 8
The formula 8 of 6 formula of formula 5
Compound shown in formula 8 is dissolved in dichloromethane, DIPEA (DIPEA) catalysis is added, adds formula 9
Shown thio phenyl chloroformate, the mol ratio of the two are 1:3,50 DEG C are heated to reflux 10h, are then filtered, obtain sterling
Formula 2
The formula 2 of 8 formula of formula 9.
Present invention also offers the probe of the present invention to prepare for detecting the purposes in sample in the preparation of ion concentration of mercury.
Application as described above, first with manufacturing probe storing solution：Weigh the compound shown in 5 mg formula 2 and be added to colorimetric cylinder
In, 1mL dichloromethane is added, is shaken up, dissolves probe, then with absolute ethyl alcohol constant volume to 10 mL, is configured to 1 mM probe
Storing solution；
Then, 5mL absolute ethyl alcohol is added in colorimetric cylinder, the probe storing solution (1 mM) for pipetting 50 μ L is put into colorimetric cylinder,
2-3mL distilled water is added, then adds 0.5 mL 4- hydroxyethyl piperazineethanesulfonic acids（HEPES）, then arrived with distilled water constant volume
10mL；Pipette 200 μ L mercury ions solution (1 mM) to add in colorimetric cylinder, shake up, after 20min, use sepectrophotofluorometer
（Horiba FluoroMax-4）Determine fluorescence spectrum.
The mercury ion fluorescence probe of the present invention can be acted on mercury ion, the change of fluorescence spectrum be produced, so as to realize to mercury
The quantitative detection of ion.
Specifically, mercury ion fluorescence probe of the invention respectively with cadmium ion, lead ion, magnesium ion, aluminium ion, ferrous iron from
Other ions such as son, ferric ion, chromium ion, calcium ion, zinc ion, sodium ion, potassium ion, cobalt ions and nickel ion are carried out
Effect can not cause the obvious change of fluorescence spectrum, so as to realize the Selective recognition to mercury ion, and then optionally use
In exclude these cadmium ions, lead ion, magnesium ion, aluminium ion, ferrous ion, ferric ion, chromium ion, calcium ion, zinc
The interference of quantitative determination of the presence of ion, sodium ion, potassium ion, cobalt ions and nickel ion to mercury ion.
The present invention mercury ion fluorescence probe Stokes shift it is very big, so as to be advantageous to reduce own absorption spectrum or from
Influence of the body fluorescence spectrum to fluorescence intensity.
Selectively, the stability of mercury ion fluorescence probe of the invention is good, and then can preserve use for a long time.
Further, mercury ion fluorescence probe of the invention is quick high-selectivity mercury ion fluorescence probe, and is synthesized simply, is had
Beneficial to commercialized popularization and application.
The invention has the advantages that the present invention relates to a kind of quick high-selectivity mercury ion fluorescence probe.Specifically, it is of the invention
Probe be a kind of thiocarbonic acid esters compound, its can as mercury ion fluorescence probe be used for mercury ion detection.This kind of spy
Pin can be realized at least one in following technique effect：Mercury ion is identified with high selectivity；Quickly mercury ion can be realized
Response；Larger Stokes shift；Property is stable, can preserve use for a long time；And there is stronger antijamming capability.
Brief description of the drawings
Fig. 1 is (5 μM) fluorescence spectrums added before and after Hg2+ (20 μM) of probe.
Influences of Fig. 2 various concentrations Hg2+ (0-40 μM) to probe (5 μM) fluorescence spectrum.
Influence of Fig. 3 different ions analyte (20 μM) to the fluorescence intensity of probe (5 μM).
Embodiment：
Below will be by the way that the present invention be described in more detail by following examples.Following examples are merely illustrative, it should
Understand, the present invention is not limited by following embodiments.
Embodiment 1：Formula 5 and the compound of formula 8
Take and the g of hexamethylenetetramine 11.2 shown in formula 4 is dissolved in 20 mL trifluoroacetic acid, add 2.16 shown in formula 3
G p-methyl phenols, the two mol ratio are 4:1,100 DEG C is heated to reflux 6 hours, and shading treatment, adds product after having reacted
Enter in frozen water, filtered after separating out solid, obtain sterling formula 5.
The formula 5 of 3 formula of formula 4
656 mg shown in modus ponens 5 are dissolved in 20 mL absolute ethyl alcohols, add the mg of amino benzenethiol 500 shown in formula 6, the two
Mol ratio is 1:1, stirring at normal temperature, 37% mg of hydrochloric acid 1184 and 30% hydrogen peroxide 2720 is added dropwise in whipping process
Mg, 30 min are reacted, are then filtered to obtain sterling formula 8.
The formula 8 of 6 formula of formula 5
Embodiment 2
The formula 2 of 8 formula of formula 9
（Scheme 1）By 374 mg（1 mmol）The compound of formula 8 is dissolved in 10mL dichloromethane made of embodiment 1, adds 129mg
（1 mmol）DIPEA, add 173 mg（1 mmol）50 DEG C of backflow 10h of thio phenyl chloroformate, then using rotating instrument
Outstanding steaming is carried out, obtains solid, the solid is the crude product of compound shown in formula 2.If obtaining purer product, will can hang
The mixed system of solid dichloromethane and petroleum ether after steaming（Such as v/v, 1:1）, obtained using silica gel column chromatography orange
Pure product 423.3mg, yield 83%.
（Scheme 2）By 374 mg（1 mmol）The compound of formula 8 is dissolved in 10mL dichloromethane made of embodiment 1, adds 387mg
（3 mmol）DIPEA, add 519 mg（3 mmol）50 DEG C of backflow 10h of thio phenyl chloroformate, then using rotating instrument
Outstanding steaming is carried out, obtains solid, the solid is the crude product of compound shown in formula 2.If obtaining purer product, will can hang
The mixed system of solid dichloromethane and petroleum ether after steaming（Such as v/v, 1:1）, obtained using silica gel column chromatography orange
Pure product 464.1mg, yield 91%.
（Scheme 3）By 374 mg（1 mmol）Compound shown in formula 8 is dissolved in 10mL dichloromethane, adds 645mg（5 mmol）
DIPEA, add 865 mg（5 mmol）50 DEG C of backflow 10h of thio phenyl chloroformate, outstanding steaming then is carried out using rotating instrument,
Solid is obtained, the solid is the crude product of compound shown in formula 2., can be by consolidating after outstanding steaming if obtaining purer product
The mixed system of body dichloromethane and petroleum ether（Such as v/v, 1:1）, orange pure product is obtained using silica gel column chromatography
443.7mg, yield 87%.
（Scheme 4）By 374 mg（1 mmol）The compound of formula 8 is dissolved in 15mL dichloromethane made of embodiment 1, is added
258mg（2 mmol）DIPEA, add 346 mg（2 mmol）Thio 50 DEG C of backflow 10h of phenyl chloroformate, then utilize rotation
Steam instrument and carry out outstanding steaming, obtain solid, the solid is the crude product of compound shown in formula 2., can be with if obtaining purer product
By the solid dichloromethane and the mixed system of petroleum ether after outstanding steaming（Such as v/v, 1:1）, obtained using silica gel column chromatography
Orange pure product 433.5mg, yield 85%.
（Scheme 5）By 374 mg（1 mmol）The compound of formula 8 is dissolved in 10mL dichloromethane made of embodiment 1, adds 387mg
（3mmol）DIPEA, add 519 mg（3 mmol）50 DEG C of backflow 15h of thio phenyl chloroformate, then entered using rotating instrument
Row is outstanding to be steamed, and obtains solid, and the solid is the crude product of compound shown in formula 2., can be by outstanding steaming if obtaining purer product
Solid dichloromethane and the mixed system of petroleum ether afterwards（Such as v/v, 1:1）, obtained using silica gel column chromatography orange pure
Net products 479.4mg, yield 94%.
The nuclear-magnetism of the mercury ion fluorescence probe of the present invention characterizes（That is hydrogen spectrum, carbon spectrum）Data are as follows：
1H-NMR (400 MHz, DMSO-d6) δ (*10-6): 2.59(s, 3H), 7.21(d, J = 8.0 Hz,
2H), 7.35(t, J = 8.0 Hz, 1H), 7.49(t, J = 8.0 Hz, 2H), 7.57(t, J = 8.0 Hz,
2H), 7.65(t, J = 8.0 Hz, 2H), 8.19(d, J = 8.0 Hz, 2H), 8.33(d, J = 8.0 Hz,
2H), 8.34 (s, 2H). 13C-NMR (100 MHz, DMSO-d6) δ (*10-6): 20.90, 115.69,
121.94, 122.97, 123.63, 126.55, 127.48, 127.73, 129.82, 130.55, 133.46,
135.56, 138.70, 145.61, 152.86, 153.62, 161.72, 193.28. ESI-MS calcd for
C28H19N2O2S3 [M + H]+ 511.1, found 511.1.
Embodiment 3
Using the compound of scheme 5, probe is prepared.Weigh the compound shown in 5 mg formula 2 to be added in colorimetric cylinder, add
1mL dichloromethane, shakes up, and dissolves probe, then with absolute ethyl alcohol constant volume to 10 mL, is configured to 1 mM probe storing solution.
Manufactured probe is used for detecting, fluorescence detection method is：5mL absolute ethyl alcohol is added in colorimetric cylinder, is pipetted
50 μ L probe storing solution (1 mM) is put into colorimetric cylinder, adds 2-3mL distilled water, then adds 0.5 mL 4- ethoxy piperazines
Piperazine ethyl sulfonic acid（HEPES）, then with distilled water constant volume to 10mL, pipette 200 μ L mercury ions solution (1 mM) and add in colorimetric cylinder.
Shake up, after 20min, use sepectrophotofluorometer（Horiba FluoroMax-4）Determine fluorescence spectrum.
Testing result is as shown in Figure 1.
Fig. 1 is probe（5µM）Add Hg2+（20 µM）Front and rear fluorescence spectrum, by illustration it may be seen that fluorescence
Change is clearly.
Embodiment 4
The probe prepared using the compound of scheme 2.Weigh the compound shown in 5 mg formula 2 to be added in colorimetric cylinder, add
1mL dichloromethane, shakes up, and dissolves probe, then with absolute ethyl alcohol constant volume to 10 mL, is configured to 1 mM probe storing solution.
The detection of fluorescence spectrum is carried out, specific method is：5mL absolute ethyl alcohol is added in colorimetric cylinder, pipettes 50 μ L's
Probe storing solution (1 mM) is put into colorimetric cylinder, adds 2-3mL distilled water, then adds 0.5 mL 4- hydroxyethyl piperazine second sulphurs
Acid（HEPES）, then with distilled water constant volume to 10mL, pipette 50-400 μ L mercury ions solution (1 mM) and add in colorimetric cylinder.Shake
It is even, after 20min, use sepectrophotofluorometer（Horiba FluoroMax-4）Determine fluorescence spectrum.
As a result it is as shown in Figure 2.
Influences of Fig. 2 various concentrations Hg2+ (0-40 μM) to probe (5 μM) fluorescence spectrum, as seen from the figure, probe (5 μM) is right
Various concentrations Hg2+ (0-16 μM) response meets good linear relationship.
As can be seen that along with the increase of Hg2+ concentration in probe solution, fluorescence intensity gradually strengthens, and at (0-16 μM)
In Hg2+ concentration ranges, response of the probe to Hg2+ concentration is linear.Therefore, probe of the invention can be relatively accurately true
Determine the content of mercury ion in sample to be tested.
Embodiment 5
Using the compound of scheme 1, probe is prepared.Weigh the compound shown in 5 mg formula 2 to be added in colorimetric cylinder, add
1mL dichloromethane, shakes up, and dissolves probe, then with absolute ethyl alcohol constant volume to 10 mL, is configured to 1 mM probe storing solution.
Manufactured probe is used for detecting, fluorescence intensity detection method is：5mL absolute ethyl alcohol is added in colorimetric cylinder, is pipetted
50 μ L probe storing solution (1 mM) is put into colorimetric cylinder, adds 2-3mL distilled water, then adds 0.5 mL 4- ethoxy piperazines
Piperazine ethyl sulfonic acid（HEPES）, then with distilled water constant volume to 10mL, pipette 200 μ L different ions analytes (1 mM) and add colorimetric cylinder
It is interior.Shake up, after 20min, use sepectrophotofluorometer（Horiba FluoroMax-4）Determine fluorescence spectrum.
As a result it is as shown in Figure 3.
Fluorescence intensity of Fig. 3 different ions analyte (20 μM) to probe (5 μM).All measure are determined after 20min, are rung
Than very fast between seasonable.
Analyte includes：Cadmium ion（Cd2+）, lead ion（Pb2+）, magnesium ion（Mg2+）, aluminium ion（Al3+）, ferrous ion
（Fe2+）, ferric ion（Fe3+）, chromium ion（Cr3+）, calcium ion（Ca2+）, zinc ion（Zn2+）, sodium ion（Na+）, potassium
Ion（K+）, cobalt ions（Co2+）And nickel ion（Ni2+）.Their concentration is 20 μM.All test conditions be distilled water,
Absolute ethyl alcohol（v/v,5:5）With 4- hydroxyethyl piperazineethanesulfonic acids（HEPES）Middle completion, used probe are made in scheme 1
Standby probe, and all spectrum measure all at 25 DEG C after analyte addition after 20min.Specifically, add in colorimetric cylinder
Enter 5mL absolute ethyl alcohol, the probe storing solution (1 mM) for pipetting 50 μ L is put into colorimetric cylinder, adds 2-3mL distilled water, then
Add 0.5 mL 4- hydroxyethyl piperazineethanesulfonic acids（HEPES）, then with distilled water constant volume to 10mL, pipette 200 μ L different ions point
Thing (1 mM) is analysed to add in colorimetric cylinder.Shake up, determined after 20min.As a result it is as shown in Figure 3.
From figure 3, it can be seen that the probe only has response to mercury ion, and common ion present in environment will not significantly interfere with spy
For the fluorescence intensity of mercury ion, therefore probe has good selectivity and anti-interference.
Shown in Fig. 3, only to contain the fluorescence intensity of following ion in analysis storing solution therein, right side is in left side
The fluorescence intensity added after Hg2+. (1) Hg2+; (2) Cd2+; (3) Pb2+; (4) Mg2+; (5) Al3+; (6)
Fe2+; (7) Fe3+; (8) Cr3+; (9) Ca2+; (10) Zn2+; (11) Na+; (12) K+; (13) Co2+;
(14) Ni2+
Although with above embodiments describing the present invention, it should be appreciated that on the premise of without departing substantially from the spirit of the present invention,
The present invention further can be modified and changed, and these modifications and variation are belonged within protection scope of the present invention.
Claims (5)
1. a kind of fluorescence probe for analyzing mercury ion, it is thiocarbonic acid esters compound, and its structure is as shown in Equation 1：
Formula 1
Wherein：R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15 are hydrogen atom, and carbon atom is
1-3 straight or branched alkyl, carbon atom be 1-3 straight or branched alkoxyl, sulfonic group, ester group, carboxyl；R1, R2, R3,
R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14 and R15 are identical or different.
2. fluorescence probe according to claim 1, it is characterized in that, structural formula is as shown in Equation 2：
Formula 2.
3. the preparation method of the fluorescence probe described in a kind of claim 2, it is characterised in that using following steps:
Hexamethylenetetramine shown in formula 4 is dissolved in 20 mL trifluoroacetic acid, adds the p-methyl phenol shown in formula 3, two
Person's mol ratio is 4:1,100 DEG C is heated to reflux 6 hours, and shading treatment, adds product in frozen water after having reacted, and separates out solid
Filtered after body, obtain sterling formula 5
The formula 5 of 3 formula of formula 4
Compound shown in formula 5 is dissolved in absolute ethyl alcohol, adds the amino benzenethiol shown in formula 6, the two mol ratio is 1:
1, stirring at normal temperature, 37% hydrochloric acid and 30% hydrogen peroxide are added dropwise in whipping process, react 30 min, then filtered
Obtain sterling formula 8
The formula 8 of 6 formula of formula 5
Compound shown in formula 8 is dissolved in dichloromethane, DIPEA (DIPEA) catalysis is added, adds formula 9
Shown thio phenyl chloroformate, the mol ratio of the two are 1:3,50 DEG C are heated to reflux 10h, are then filtered, obtain sterling
Formula 2
The formula 2 of 8 formula of formula 9.
4. a kind of fluorescence probe of claim 1 or 2 is being prepared for detecting the use in sample in the preparation of ion concentration of mercury
On the way.
5. application according to claim 4, it is characterised in that：
Match somebody with somebody manufacturing probe storing solution first：Weigh the compound shown in 5 mg formula 2 to be added in colorimetric cylinder, add 1mL dichloro
Methane, shake up, dissolve probe, then with absolute ethyl alcohol constant volume to 10 mL, be configured to 1 mM probe storing solution；
Then, 5mL absolute ethyl alcohol is added in colorimetric cylinder, the probe storing solution (1 mM) for pipetting 50 μ L is put into colorimetric cylinder,
2-3mL distilled water is added, then adds 0.5 mL 4- hydroxyethyl piperazineethanesulfonic acids（HEPES）, then arrived with distilled water constant volume
10mL；Pipette 200 μ L mercury ions solution (1 mM) to add in colorimetric cylinder, shake up, after 20min, use sepectrophotofluorometer
（Horiba FluoroMax-4）Determine fluorescence spectrum.
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| CN108728085A (en) * | 2018-05-28 | 2018-11-02 | 郑州大学 | A kind of preparation method and applications of the luminous carbon dots probe of ratio |
| CN111635376A (en) * | 2020-06-10 | 2020-09-08 | 上海海关工业品与原材料检测技术中心 | Trivalent As detection probe, preparation method and application thereof |
| CN112442357A (en) * | 2019-09-03 | 2021-03-05 | 北京工商大学 | Double-reaction-site fluorescent probe |
| CN112442358A (en) * | 2019-09-03 | 2021-03-05 | 北京工商大学 | Benzothiazole type mercury ion fluorescent probe |
| CN112441955A (en) * | 2019-09-03 | 2021-03-05 | 北京工商大学 | Three-recognition-site fluorescent probe |
| CN112441954A (en) * | 2019-09-03 | 2021-03-05 | 北京工商大学 | Mercury ion fluorescent probe with double recognition sites |
| CN115894421A (en) * | 2022-11-09 | 2023-04-04 | 南京林业大学 | Hg is discerned to high selectivity 2+ Flavonol thiocarbonate fluorescent probe and preparation method and application thereof |
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Application publication date: 20171110 |