CN107298664A - A kind of colorimetric fluorescence probe for analyzing mercury ion, preparation method and application - Google Patents
A kind of colorimetric fluorescence probe for analyzing mercury ion, preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of high selectivity mercury ion colorimetric fluorescence probe.Specifically, probe of the invention is a class thiocarbonic acid esters compound, and it can be used for the detection of mercury ion as mercury ion colorimetric fluorescence probe.This kind of probe can realize at least one in following technique effect：Mercury ion is recognized with high selectivity；Mercury ion can be realized faster and responded；Good water solubility；Property is stable, can for a long time preserve and use；And with stronger antijamming capability.
Description
Technical field
, can be to mercury ion high selection personality the present invention relates to thiocarbonic acid esters compound as mercury ion fluorescence probe
Quick identification, or its can in determination sample mercury ion concentration.
Background technology
Mercury is unique liquid metal under normal temperature, normal pressure, is than a kind of sparser element, the mercury of only a few in the earth's crust
Exist in its natural state with the state of metal simple-substance.The purposes of mercury has a lot, can be not only used for manufacturing measuring instrument, such as temperature
Spend meter, sphygmomanometer etc.；It can be also used for manufacturing insecticide；It can be used for extracting other noble metals from mineral reserve（Gold）Deng.
But mercury is as a Heavy Metallic Elements, its harm to environment and human body is equally very important.Mercury pollution it is main
Source includes the waste water of the industry such as burning, instrucment and meter plant, smelting noble metal of solid waste.Because mercury is that one kind biological can not drop
Element is solved, there is very strong migration and bioaccumulation again, mercury element and its compound can be entered by skin or food chain
Enter human body, and can not normally be metabolized and excrete, therefore harm can be produced to brain, liver and nervous system etc..In recent years
Come, mercury pollution turns into a global 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 Optical Analysis Method, volumetric analysis, mercury ion selection electrode method, chromatography of ions
The methods such as method (IC).Colorimetric fluorescence probe turns into researcher due to its distinctive advantage in these numerous detection methods
Focus of attention.However, the fluorescence probe reported at present still suffers from some problems, including selectivity not enough good, response speed is not
Enough fast, synthesis are complicated.Due to other ions in environment such as cobalt ions, potassium ion, tin ion, sodium ion, nickel ion, lead from
Son, chromium ion, calcium ion, magnesium ion, cadmium ion, ferrous ion, zinc ion, copper ion, ferric ion and aluminium ion etc.
Other metal ions, it can constitute potential interference to the detection of mercury ion, therefore, and development synthesis is simple, good water solubility, highly sensitive
Degree, the mercury ion colorimetric fluorescence probe of high selectivity are the problems that those skilled in the art are badly in need of solving.
The content of the invention
This area is badly in need of one kind and prepares simple high selectivity mercury ion colorimetric fluorescence probe, so as to effective detection mercury
Ion.Therefore, the present invention has synthesized the colorimetric fluorescence probe of the novel mercury ion of a class, it is high, water-soluble that it synthesizes simple, selectivity
Property is good.Present invention also offers the preparation method of above-mentioned colorimetric fluorescence probe, and preparing for detecting mercury ion in sample
Application in the preparation of concentration.
The present invention is realized by following measures
Specifically, the invention provides a kind of mercury ion colorimetric fluorescence probe, it is thiocarbonic acid esters compound, its structure
As shown in Equation 1：
Formula 1
In above formula：R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 are hydrogen atom, carbon number 1-3 straight or branched
Alkyl, carbon number 1-3 straight or branched alkoxyl, sulfonic group, ester group, carboxyl；R1, R2, R3, R4, R5, R6, R7, R8,
R9, R10, R11 are identical or different.
It is preferred that, fluorescence probe of the invention, its structure is as shown in Equation 2：
Formula 2.
Present invention also offers the preparation method of mercury ion fluorescence probe, it is characterised in that uses following steps:
Parahydroxyben-zaldehyde shown in formula 6 is dissolved in dichloromethane, the thio phenyl chloroformate shown in formula 5 is added, the two
Mol ratio is 1:1.5, under DIPEA (DIPEA) catalytic action, then stirring at normal temperature 10h carries out suction filtration,
Obtain sterling formula 3
The formula 3 of 5 formula of formula 6
3-OH-3-CH3-2 butanone shown in formula 7 is dissolved in pyridine, plus 2-3 drop acetic acid, the malononitrile shown in formula 8, two is added
The mol ratio of person is 1:2,24h is reacted in 25 DEG C of oil baths, suction filtration is then carried out, sterling formula 4 is obtained
The formula 4 of 7 formula of formula 8
Carbonats compound shown in formula 3 is dissolved in absolute ethyl alcohol, under the catalytic action of piperazine, added shown in formula 4
Nitrile, the mol ratio of the two is 1:1, stirring at normal temperature 10h, then carry out suction filtration, obtain the sterling shown in formula 2；
The formula 2 of 3 formula of formula 4
It is preferred that, the probe for corresponding to the present invention of the invention is corresponding thiocarbonic acid esters compound.
Present invention also offers the method for ion concentration of mercury in detection sample, it includes the probe of the present invention and treats test sample
The step of this contact.
Prepared present invention also offers the probe of the present invention for detecting the application in sample in the preparation of ion concentration of mercury.
Application as described above, first with manufacturing probe storing solution：The formula 2 for weighing 5 mg is added in colorimetric cylinder, adds the two of 1mL
Chloromethanes, shakes up, and dissolves probe, then with absolute ethyl alcohol constant volume to 10 mL, is configured to 1 mM probe storing solution.
Then, 1mL absolute ethyl alcohol is added in colorimetric cylinder, the probe storing solution (1mM) for pipetting 50 μ L is put into colorimetric cylinder,
4-6mL distilled water is added, 0.5 mL phosphate buffered saline solution PBS is then added, then pipetted to 10mL with distilled water constant volume
200 μ L mercury ions solution (1 mM) are added in colorimetric cylinder, are shaken up, after 40min, are used sepectrophotofluorometer（Horiba
FluoroMax-4）Determine fluorescence spectrum.
Application as described above, first with manufacturing probe storing solution：Match somebody with somebody manufacturing probe storing solution first：The formula 2 for weighing 5 mg is added to
In colorimetric cylinder, 1mL dichloromethane is added, shakes up, dissolves probe, then 1 mM is configured to 10 mL with absolute ethyl alcohol constant volume
Probe storing solution.
Then, 1mL absolute ethyl alcohol is added in colorimetric cylinder, the probe storing solution (1 mM) for pipetting 50 μ L is put into colorimetric cylinder,
4-6mL distilled water is added, 0.5 mL phosphate buffered saline solution PBS is then added, then pipetted to 10mL with distilled water constant volume
200 μ L mercury ions solution (1 mM) are added in colorimetric cylinder, are shaken up, after 40min, are used ultraviolet-visible spectrophotometer（UV-
3101PC）Determine absorption spectrum.
The mercury ion colorimetric fluorescence probe of the present invention can be acted on mercury ion, produce fluorescence spectrum and ultra-violet absorption spectrum
Change, so as to realize the quantitative detection to mercury ion.
Specifically, mercury ion fluorescence probe of the invention respectively with cobalt ions, potassium ion, tin ion, sodium ion, nickel ion,
Lead ion, chromium ion, calcium ion, magnesium ion, cadmium ion, ferrous ion, zinc ion, copper ion, ferric ion and aluminium from
Son waits other ions to be acted on and can not cause the obvious change of fluorescence spectrum and ultra-violet absorption spectrum, thus realize to mercury from
The Selective recognition of son, and then can be optionally used for excluding these cobalt ions, potassium ion, tin ion, sodium ion, nickel ion, lead
Ion, chromium ion, calcium ion, magnesium ion, cadmium ion, ferrous ion, zinc ion, copper ion, ferric ion and aluminium ion
Interference of the presence to the quantitative determination of mercury ion.
The mercury ion fluorescence probe mercury ion reaction of the present invention is very sensitive, so as to be conducive to the rapid detection to mercury ion.
Selectively, the stability of mercury ion fluorescence probe of the invention is good, and then can for a long time preserve and use.
Further, mercury ion fluorescence probe of the invention is high selectivity mercury ion colorimetric fluorescence probe, and synthesis is simple, water
Dissolubility is good, is conducive to commercialized popularization and application.
The beneficial effects of the invention are as follows prepare simple, high selectivity, the compound of good water solubility the invention provides a kind of
The mercury ion colorimetric fluorescence probe being made, so as to effective detection mercury ion.The preparation method of the present invention, its synthesize it is simple,
Condition temperature closes, is suitable for industrialized production.The present invention is being prepared for detecting the application in sample in the preparation of ion concentration of mercury,
With good water solubility, sensitivity is high, and measuring method is simple and reliable, high selectivity can recognize mercury ion and in ring faster
Quantitative analysis accurately can be carried out to mercury ion in the presence of other ions in border.
Brief description of the drawings
Fig. 1 is the fluorescence spectrum that (5 μM) of probe is added before and after Hg2+ (20 μM)
Fig. 2 is the absorption spectrum that (5 μM) of probe is added before and after Hg2+ (20 μM).
Influences of Fig. 3 various concentrations Hg2+ (0-20 μM) to probe (5 μM) fluorescence spectrum.
Influence of Fig. 4 different ions analyte (20 μM) to the fluorescence intensity of probe (5 μM).
Influence of Fig. 5 different ions analyte (20 μM) to the fluorescence intensity of probe (5 μM) (added with Hg2+).
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 3 and the compound of formula 4
The mg of parahydroxyben-zaldehyde 244 shown in modus ponens 6 is dissolved in 15mL dichloromethane, adds the thio chloromethane shown in formula 5
The mg of acid phenenyl ester 519, the mol ratio of the two is 1:1.5, make in the catalysis of 120 mg DIPEAs (DIPEA)
Under, then stirring at normal temperature 10h carries out suction filtration, obtains sterling formula 3.
The formula 3 of 5 formula of formula 6
The mg of 3-OH-3-CH3-2 butanone 306 shown in modus ponens 7 is dissolved in pyridine, plus 2-3 drop acetic acid, adds third shown in formula 8
The mg of dintrile 396, the mol ratio of the two is 1:2,24h is reacted in 25 DEG C of oil baths, suction filtration is then carried out, sterling formula 4 is obtained
The formula 4 of 7 formula of formula 8
Embodiment 2
The formula 2 of 3 formula of formula 4
（Scheme 1）By 199 mg（1 mmol）Carbonats compound shown in formula 3 is dissolved in 15mL absolute ethyl alcohols, is added a piece of
Piperazine（86g/mol）, add 258 mg（1 mmol）Then nitrile shown in formula 4, stirring at normal temperature 10h carries out suction filtration, obtains
To sterling 364.8mg, yield is 83%.
（Scheme 2）By 198 mg（1 mmol）Carbonats compound shown in formula 3 is dissolved in 15mL absolute ethyl alcohols, is added a piece of
Piperazine（86g/mol）, add 337 mg（1.3 mmol）Then nitrile shown in formula 4, stirring at normal temperature 10h carries out suction filtration,
Sterling 400.0mg is obtained, yield is 91%.
（Scheme 3）By 198 mg（1 mmol）Carbonats compound shown in formula 3 is dissolved in 15mL absolute ethyl alcohols, is added a piece of
Piperazine（86g/mol）, add 389 mg（1.5 mmol）Then nitrile shown in formula 4, stirring at normal temperature 10h carries out suction filtration,
Sterling 373.6mg is obtained, yield is 85%.
（Scheme 4）By 198 mg（1 mmol）Carbonats compound shown in formula 3 is dissolved in 20mL absolute ethyl alcohols, is added
A piece of piperazine（86g/mol）, add 518 mg（2 mmol）Then nitrile shown in formula 4, stirring at normal temperature 10h carries out taking out
Filter, obtains sterling 386.8mg, yield is 88%.
（Scheme 5）By 198 mg（1 mmol）Carbonats compound shown in formula 3 is dissolved in 15mL absolute ethyl alcohols, is added
A piece of piperazine（86g/mol）, add 337 mg（1.3 mmol）Nitrile shown in formula 4, stirring at normal temperature 15h, is then taken out
Suction filtration, obtains sterling 408.7mg, and yield is 93%.
The nuclear-magnetism of the mercury ion colorimetric probe of the present invention is characterized（I.e. hydrogen spectrum, carbon are composed）Data are as follows：
1H NMR (400 MHz, DMSO-d6 ) δ (× 10-6): 1.82 (s, 6H), 7.27 (d, J = 16.0
Hz, 1H), 7.35-7.40 (m, 3H), 7.50-7.55 (m, 3H), 7.60 (d, J = 8.0 Hz, 1H), 7.95
(d, J = 16.0 Hz, 1H), 8.06-8.09 (m, 2H). 13C NMR (100 MHz, DMSO-d6 ) δ (×10-
6): 25.53, 55.23, 99.99, 100.53, 101.81, 104.12, 111.21, 112.25, 116.59,
122.17, 123.39, 127.57, 130.41, 131.54, 133.65, 146.24, 153.61, 155.80,
157.53, 175.41, 177.52, 186.22, 192.49, 194.12.
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.
The probe being made is used for detect, fluorescence detection method is：1mL absolute ethyl alcohol is added in colorimetric cylinder, 50 μ L are pipetted
Probe storing solution (1 mM) put into colorimetric cylinder, add 4-6mL distilled water, the phosphate-buffered salt for then adding 0.5 mL is molten
Liquid PBS, then with distilled water constant volume to 10mL, pipette 200 μ L mercury ions solution (1 mM) and add in colorimetric cylinder.Shake up, 40min
Afterwards, sepectrophotofluorometer is used（Horiba FluoroMax-4）Determine fluorescence spectrum.
Absorption spectrum detection method is：1mL absolute ethyl alcohol is added in colorimetric cylinder, 50 μ L probe storing solution (1 is pipetted
MM) put into colorimetric cylinder, add 4-6mL distilled water, then add 0.5 mL phosphate buffered saline solution PBS, then use distilled water
Constant volume pipettes 200 μ L mercury ions solution (1 mM) and added in colorimetric cylinder to 10mL.Shake up, after 40min, with ultraviolet-visible point
Light photometer（UV-3101PC）Determine absorption spectrum.
Testing result is as depicted in figs. 1 and 2.
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.
Fig. 2 is probe（5 µM）Add Hg2+（20 µM）Front and rear absorption spectrum, by illustration, we can clearly see
To the change of absorption spectrum, and the change for passing through color, it is possible to achieve naked eye.Color change is in figure：It is before addition
Yellow, after addition, color is changed into pink colour.
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：1mL absolute ethyl alcohol is added in each colorimetric cylinder respectively, is moved
Take 50 μ L probe storing solution (1 mM) to put into colorimetric cylinder, add 4-6mL distilled water, the phosphoric acid for then adding 0.5 mL delays
Salting liquid PBS is rushed, then with distilled water constant volume to 10mL, pipettes 5-200 μ L mercury ions solution (1 mM) and is separately added into colorimetric cylinder
It is interior, shake up, after 40min, use sepectrophotofluorometer（Horiba FluoroMax-4）Determine fluorescence spectrum.
As a result it is as shown in Figure 3.
Influences of Fig. 3 various concentrations Hg2+ (0-20 μM) to probe (5 μM) fluorescence spectrum, as seen from the figure, probe (5 μM) is right
Various concentrations Hg2+ (0-5 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 in (0-5 μM) Hg2
In+concentration range, response of the probe to Hg2+ concentration is linear.Therefore, probe of the invention can be determined relatively accurately
The content of mercury ion in sample to be tested.
Embodiment 4
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.
The probe being made is used for detect, fluorescence intensity detection method is：1mL absolute ethyl alcohol is added in colorimetric cylinder, is pipetted
50 μ L probe storing solution (1 mM) is put into colorimetric cylinder, is added 4-6mL distilled water, is then added 0.5 mL phosphoric acid buffer
Salting liquid PBS, then with distilled water constant volume to 10mL, pipette 200 μ L different ions analytes (1 mM) and add in colorimetric cylinder.Shake
It is even, after 40min, use sepectrophotofluorometer（Horiba FluoroMax-4）Determine fluorescence spectrum.
As a result as shown in Figure 4 and Figure 5.
Fig. 4 and Fig. 5 is fluorescence intensity of the different ions analyte (20 μM) to probe (5 μM).After all measure are all 40min
Determine.
Analyte includes：Cobalt ions（Co2+）, potassium ion（K+）, tin ion（Sn2+）, sodium ion（Na+）, nickel ion
（Ni2+）, lead ion（Pb2+）, chromium ion（Cr3+）, calcium ion（Ca2+）, magnesium ion（Mg2+）, cadmium ion（Cd2+）, divalence
Iron ion（Fe2+）, zinc ion（Zn2+）, copper ion（Cu2+）, ferric ion（Fe3+）And aluminium ion（Al3+）.They
Concentration is 20 μM.All test conditions are distilled water, absolute ethyl alcohol（v/v,9:1）Completed with phosphate buffered saline solution PBS,
Used probe is prepared probe in scheme 1, and all spectrum are all after analyte is added at 25 DEG C after 40min
Measure.Specifically, 1mL absolute ethyl alcohol is added in colorimetric cylinder, the probe storing solution (1 mM) for pipetting 50 μ L puts colorimetric into
Guan Zhong, adds 4-6mL distilled water, then adds 0.5 mL phosphate buffered saline solution PBS, then with distilled water constant volume to 10mL,
The above-mentioned different ions analyte storing solutions (1mM) of 200 μ L are pipetted to add in colorimetric cylinder.Shake up, determined after 40min.As a result as schemed
Shown in 3.
As can be seen from Figure 4 and Figure 5, the probe only has response to mercury ion, and common ion present in environment will not
Fluorescence intensity of the probe to mercury ion is significantly interfered with, therefore probe has good selectivity and anti-interference.
Shown in Fig. 4, contain following ion in analysis storing solution therein.(1) Hg2+; (2) Co2+; (3) K
+; (4) Sn4+; (5) Na+; (6) Ni2+; (7) Pb2+; (8) Cr3+; (9) Ca2+; (10) Mg2+; (11)
Cd2+; (12) Fe2+; (13) Zn2+; (14) Cu2+;(15) Fe3+；(16) Al3+
Shown in Fig. 5, in analysis storing solution therein in addition to containing following ion, also contain Hg2+；(1) Hg2+; (2)
Co2+; (3) K+; (4) Sn4+; (5) Na+; (6) Ni2+; (7) Pb2+; (8) Cr3+; (9) Ca2+; (10)
Mg2+; (11) Cd2+; (12) Fe2+; (13) Zn2+; (14) Cu2+;(15) Fe3+；(16) Al3+.
Although with above embodiments describing the present invention, it should be appreciated that on the premise of the spirit without departing substantially from 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 (6)
1. one kind analysis mercury ion colorimetric fluorescence probe, it is thiocarbonic acid esters compound, and its structure is as shown in Equation 1：
Formula 1
In above formula：R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 are hydrogen atom, carbon number 1-3 straight or branched
Alkyl, carbon number 1-3 straight or branched alkoxyl, sulfonic group, ester group, carboxyl；R1, R2, R3, R4, R5, R6, R7, R8,
R9, R10, R11 are identical or different.
2. colorimetric fluorescence probe according to claim 1, it is characterised in that structure is as shown in Equation 2：
Formula 2.
3. the preparation method of the colorimetric fluorescence probe described in a kind of claim 2, it is characterised in that use following steps:
Parahydroxyben-zaldehyde shown in formula 6 is dissolved in dichloromethane, the thio phenyl chloroformate shown in formula 5 is added, the two
Mol ratio is 1:1.5, under DIPEA (DIPEA) catalytic action, then stirring at normal temperature 10h carries out suction filtration,
Obtain sterling formula 3
The formula 3 of 5 formula of formula 6
3-OH-3-CH3-2 butanone shown in formula 7 is dissolved in pyridine, plus 2-3 drop acetic acid, the malononitrile shown in formula 8, two is added
The mol ratio of person is 1:2,24h is reacted in 25 DEG C of oil baths, suction filtration is then carried out, sterling formula 4 is obtained
The formula 4 of 7 formula of formula 8
Carbonats compound shown in formula 3 is dissolved in absolute ethyl alcohol, under the catalytic action of piperazine, added shown in formula 4
Nitrile, the mol ratio of the two is 1:1, stirring at normal temperature 10h, then carry out suction filtration, obtain the sterling shown in formula 2；
The formula 2 of 3 formula of formula 4.
4. colorimetric fluorescence probe described in a kind of claim 1 or 2 is being prepared for detecting in sample in the preparation of ion concentration of mercury
Application.
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, shakes up, and dissolves probe, then with absolute ethyl alcohol constant volume to 10 mL, is configured to 1 mM probe storing solution；
Then, 1mL absolute ethyl alcohol is added in colorimetric cylinder, the probe storing solution (1mM) for pipetting 50 μ L is put into colorimetric cylinder,
4-6mL distilled water is added, 0.5 mL phosphate buffered saline solution PBS is then added, then pipetted to 10mL with distilled water constant volume
200 μ L mercury ions solution (1 mM) are added in colorimetric cylinder, are shaken up, after 40min, are used sepectrophotofluorometer（Horiba
FluoroMax-4）Determine fluorescence spectrum.
6. application according to claim 4, it is characterised in that：
Match somebody with somebody manufacturing probe storing solution first：Match somebody with somebody manufacturing probe storing solution first：Weigh the compound shown in 5 mg formula 2 and be added to colorimetric
Guan Zhong, adds 1mL dichloromethane, shakes up, dissolve probe, then with absolute ethyl alcohol constant volume to 10 mL, be configured to 1 mM spy
Pin storing solution；
Then, 1mL absolute ethyl alcohol is added in colorimetric cylinder, the probe storing solution (1 mM) for pipetting 50 μ L is put into colorimetric cylinder,
4-6mL distilled water is added, 0.5 mL phosphate buffered saline solution PBS is then added, then pipetted to 10mL with distilled water constant volume
200 μ L mercury ions solution (1 mM) are added in colorimetric cylinder, are shaken up, after 40min, are used ultraviolet-visible spectrophotometer（UV-
3101PC）Determine absorption spectrum.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN112442358B (en) * | 2019-09-03 | 2022-05-17 | 北京工商大学 | Benzothiazole type mercury ion fluorescent probe |
| CN112441955B (en) * | 2019-09-03 | 2022-05-17 | 北京工商大学 | Three-recognition-site fluorescent probe |
| CN112441955A (en) * | 2019-09-03 | 2021-03-05 | 北京工商大学 | Three-recognition-site fluorescent probe |
| 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 |
| CN112442357B (en) * | 2019-09-03 | 2022-05-17 | 北京工商大学 | Double-reaction-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 |
| CN112441954B (en) * | 2019-09-03 | 2022-05-17 | 北京工商大学 | Mercury ion fluorescent probe with double recognition sites |
| CN110590784A (en) * | 2019-09-17 | 2019-12-20 | 华东理工大学 | Derivative based on pyrrolopyrroledione and preparation method and application thereof |
| CN110590784B (en) * | 2019-09-17 | 2022-01-07 | 华东理工大学 | Derivative based on pyrrolopyrroledione and preparation method and application thereof |
| CN115073338A (en) * | 2022-07-14 | 2022-09-20 | 济南大学 | High-selectivity mercury ion recognition fluorescent probe, preparation method and application |
| CN115073338B (en) * | 2022-07-14 | 2024-05-24 | 济南大学 | Fluorescent probe for high-selectivity recognition of mercury ions, preparation method and application |
| 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 |
| CN115894421B (en) * | 2022-11-09 | 2023-10-17 | 南京林业大学 | High-selectivity Hg identification 2+ Flavonol thiocarbonate fluorescent probe as well as preparation method and application thereof |
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