CN108570029A - A kind of two-photon fluorescence probe of highly selective Sensitive Detection mercury - Google Patents
A kind of two-photon fluorescence probe of highly selective Sensitive Detection mercury Download PDFInfo
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- CN108570029A CN108570029A CN201810544005.9A CN201810544005A CN108570029A CN 108570029 A CN108570029 A CN 108570029A CN 201810544005 A CN201810544005 A CN 201810544005A CN 108570029 A CN108570029 A CN 108570029A
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- C—CHEMISTRY; METALLURGY
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- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The present invention relates to a kind of two-photon fluorescence probes of highly selective Sensitive Detection mercury.Specifically, probe of the invention is 3 acetocoumarin class compound of a kind of 7 hydroxyl, can be used as detection of the mercury ion colorimetric fluorescence probe for mercury ion.This kind of probe can realize following at least one of technique effect:Mercury ion is identified with high selectivity;The High Sensitive Analysis to mercury ion may be implemented;Property is stablized, and can be used with long-term preservation;And there is stronger anti-interference ability.
Description
Technical field
The present invention relates to 7- hydroxyl -3- acetocoumarin class compounds as mercury ion fluorescence probe, can be to mercury ion
Highly selective sensitive identification or its can in determination sample mercury ion concentration.
Background technology
Mercury is a kind of metallic element with serious physiological-toxicity, since it is with persistence, property easy to migrate and height
Bioconcentration becomes one of environmental contaminants most noticeable at present.Inorganic mercury ion in environment can be certain
Under the conditions of by organism conversion be severe toxicity methyl mercury.Inorganic mercury mainly influences kidney, and methyl mercury is mainly invaded after entering human body
Evil nervous system, especially central nervous system.Both can be highly enriched in biological tissue by food chain, to people
Huge harm is caused with nature.Mercury poisoning can generate extremely ill effect, present mercury to entire society and be existed by dominated column
On global environment monitoring system inventory, therefore, to the in situ, real-time, online of the Selective recognition of mercury ion, especially mercury ion
Monitoring is all of great significance for medicine, biology and environmental science.
In consideration of it, development can effectively detect the analysis method that can especially detect mercury ion under the conditions of physiological level
It is of crucial importance and significant.Nowadays the analysis method for the detection mercury ion reported includes Atomic absorption-emission spectrum
Method, high performance liquid chromatography, inductivity coupled plasma mass spectrometry, nuclear magnetic resonance, colorimetric method (such as traditional dithizone method), electrification
Method (such as anodic stripping voltammetry, redox potentiometry), the colorimetric fluorescence probe in these numerous detection methods
It is researcher's focus of attention since its peculiar advantage forms.However, the colorimetric reported at present and fluorescence probe there are still
Some problems, including selectivity is not good enough, response speed is not fast enough, synthesis is complicated.Due to other ions such as carbon in life entity
Sour hydrogen radical ion, sulfate ion, bromide ion, chlorion, nitrate ion, nitrite ion and phosphate anion etc. other
Metal ion, it can to the detection of mercury ion constitute potential interference, therefore, development can high sensitivity detection life entity in mercury from
The analysis method of son is necessary.In short, development is quick, highly selective, highly sensitive, the simple mercury ion colorimetric fluorescence of synthesis
Binary channels probe is that those skilled in the art are badly in need of solving.
Invention content
This field be badly in need of it is a kind of preparing simple highly sensitive highly selective mercury ion fluorescence probe, so as to effective
Detect mercury ion.For this purpose, the present invention has synthesized the two-photon fluorescence probe of a kind of novel detection mercury ion, synthesis is simple,
The good, high sensitivity of selectivity.It is that 7- hydroxyl -3- acetyl is fragrant specifically, the present invention provides a kind of mercury ion fluorescence probe
Beans chlorins compound, structure are as follows:
Preferably, fluorescence probe of the invention is:
It is the probe by the way that the present invention will be corresponded to the present invention also provides the preparation method of mercury ion fluorescence probe
The DIPEA in dichloromethane solution is catalyzed corresponding examination 7- hydroxyl -3- acetocoumarin class compounds with thio phenyl chloroformate
Under the conditions of stirring at normal temperature 4 hours and synthesize and be made.
The present invention also provides the detection preparations or kit for detecting ion concentration of mercury in sample, and it includes the present invention
Probe.Preferably, detection preparation of the invention or kit also include the operation instructions of product.It is further preferred that of the invention
Kit also include buffer for measuring the ion concentration of mercury in sample.
The mercury ion fluorescence probe of the present invention can be acted on mercury ion, generate fluorescence spectrum and ultra-violet absorption spectrum
Variation, to realize the quantitative detection to mercury ion.
Specifically, the present invention mercury ion fluorescence probe respectively with potassium ion, sodium ion, calcium ion, magnesium ion, zinc from
Son, aluminium ion, nickel ion, lead ion, cadmium ion, copper ion, fluorine ion, chlorion, bromide ion, carbanion, sulfate radical
Ion, nitrate ion and nitrite ion etc., which are acted on, cannot lead to the apparent of fluorescence spectrum and ultra-violet absorption spectrum
Change, to realize to the Selective recognition of mercury ion, and then can be optionally used for excluding in these ions and life entity it
Interference of the presence of his ion to the quantitative determination of mercury ion.
Selectively, the stability of mercury ion fluorescence probe of the invention is good, and then being capable of long-term preservation use.
Further, mercury ion fluorescence probe of the invention is the high two-photon fluorescence probe of sensitivity, and synthesizes letter
It is single, be conducive to commercialized popularization and application.
Description of the drawings
Fig. 1 a are various concentration Hg2+(0,0.05,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,1,1.5,2 μM) is right
The influence of probe (5 μM) fluorescence spectrum;Fig. 1 b are various concentration Hg2+(0-2 μM) is to probe (5 μM) between fluorescence intensity and concentration
Linear relationship chart.
Fig. 2 a are mercury ion (5 μM) and other different ions analytes (25 μM) respectively to the fluorescence spectrum of probe (5 μM)
Influence.Fig. 2 b are other different ions analytes (25 μM) respectively to mercury ion (5 μM) and probe (5 μM) in 455nm wavelength
The influence of the fluorescence intensity at place.1. mercury ion, 2. potassium ions, 3. sodium ions, 4. calcium ions, 5. magnesium ions, 6. zinc ions, 7. aluminium
Ion, 8. nickel ions, 9. lead ions, 10. cadmium ions, 11. copper ions, 12. fluorine ions, 13. chlorions, 14. bromide ions, 15.
Carbanion, 16. sulfate ions, 17. nitrate ions, 18. nitrite ions.
Fig. 3 is Hg2+The influence of (5 μM) to the ultraviolet spectra of probe (5 μM).
Specific implementation mode:
The present invention provides synthetic route, method and its spectrum properties of above-mentioned highly selective mercury ion fluorescence probe.
The mercury ion fluorescence probe of the present invention is a kind of 7- hydroxyls -3- acetocoumarin class compounds, with following knot
Structure general formula
In above formula:R1, R2, R3And R4For hydrogen atom, linear or branched alkyl group, straight or branched alkoxyl, sulfonic group, ester
Base, carboxyl;R1, R2, R3And R4It can be identical or different.
The synthetic route and method of such mercury ion fluorescent fluorescence probe are as follows:
Specifically, colorimetric fluorescence probe of the invention can be prepared via a method which, by certain mol proportion (example 1: 1.5-
1: 3) 7- hydroxyl -3- acetocoumarins are dissolved in thio phenyl chloroformate in dichloromethane, the molar ratio of the two is that (1: 2) is right
Afterwards stirring at normal temperature for a period of time (such as 4h), then using revolving instrument rotated, be added after being spin-dried for a small amount of dichloromethane by its
Dissolving obtains product after crossing column, if to obtain purer product, it can be used to the mixed system of dichloromethane and petroleum ether
(such as v/v, 1: 10) carrying out being recrystallized to give sterling.
Therefore, the use the present invention also provides thio phenyl chloroformate in preparing the fluorescence probe for detecting mercury ion
On the way.
The present invention also provides use of the 7- hydroxyl -3- acetocoumarins in preparing the fluorescence probe for detecting mercury ion
On the way.
The highly selective highly sensitive identification mercury ion colorimetric fluorescence probe of the present invention is noteworthy characterized by being capable of quick Gao Xuan
It selects the quick identification mercury ion of personality and can quantitative analysis accurately be carried out to mercury ion in the presence of other ions.
It below will be by the way that the present invention be described in more detail by following embodiment.Following embodiment is merely illustrative,
It should be understood that the present invention is not limited by following embodiments.
Embodiment 1
300mg (1.47mmol) 7- hydroxyl -3- acetocoumarins are dissolved in 15mL dichloromethane, 635mg is added
Then (3.68mmol) thio phenyl chloroformate stirring at normal temperature 4h is rotated using revolving instrument, obtains crude product.If obtained
To purer product, can be crossed column then dichloromethane and petroleum ether mixed system (such as v/v, 1: 10) being carried out in
It is recrystallized to give sterling.Obtain white pure product 231mg, yield 46%.
1H NMR demonstrate the correctness of product structure.
Embodiment 2
Fig. 1 a are various concentration Hg2+(0,0.05,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,1,1.5,2 μM) is right
The influence of probe (5 μM) fluorescence spectrum;Fig. 1 b are various concentration Hg2+(0-2 μM) is to probe (5 μM) between fluorescence intensity and concentration
Linear relationship chart.
It can be seen that be added mercury ion before and after change in fluorescence clearly.Along with Hg in probe solution2+The increase of concentration,
Fluorescence intensity gradually increases, and in (0-2 μM) Hg2+In concentration range, Hg2+Concentration and fluorescence intensity closed at linear well
System.Illustrate that probe has good response to mercury ion, which can realize the sensitive identification to mercury ion.Drinking Water in China standard
Therefore for 0.001mg/L, probe of the invention can relatively accurately determine mercury ion in sample to be tested to the standard limited value of middle mercury ion
Content.
Embodiment 3
Fig. 2 a are mercury ion (5 μM) and other different ions analytes (25 μM) respectively to the fluorescence spectrum of probe (5 μM)
Influence.Fig. 2 b are other different ions analytes (25 μM) respectively to mercury ion (5 μM) and probe (5 μM) in 455nm wavelength
The influence of the fluorescence intensity at place.
Analyte includes:1. mercury ion, 2. potassium ions, 3. sodium ions, 4. calcium ions, 5. magnesium ions, 6. zinc ions, 7. aluminium
Ion, 8. nickel ions, 9. lead ions, 10. cadmium ions, 11. copper ions, 12. fluorine ions, 13. chlorions, 14. bromide ions, 15.
Carbanion, 16. sulfate ions, 17. nitrate ions, 18. nitrite ions, in addition to ion concentration of mercury is 5 μM,
It is 25 μM that it, which analyzes ion concentration,.All test conditions are completed in pure water, and used probe is made in embodiment 1
Standby probe, and the analyte addition all at 25 DEG C of all spectrum measures after sixty minutes.Specifically, the 1mM of 50 μ L is pipetted
Probe storing solution is put into 10mL colorimetric cylinders, and the HEPES buffer solutions of 5mL pure water and the PH 7.4 of 0.5mL are then added, and use is pure
Water is settled to 10mL, then pipettes the above-mentioned 10mM analytes storing solution of different volumes and be added in colorimetric cylinder, shakes up, is measured after 60min.
The results are shown in Figure 2.
Can be seen that existing other common ions in organism from Fig. 2 a will not have probe apparent response;From figure
2b can be seen that the fluorescence intensity that existing other common ions will not significantly interfere with probe to mercury ion in organism, therefore
Probe has good selectivity.
Embodiment 4
Fig. 3 is Hg2+The influence of (5 μM) to the ultraviolet spectra of probe (5 μM).Specifically, pipetting the 1mM probe deposits of 50 μ L
Liquid is put into 10mL colorimetric cylinders, and 10mL is dissolved to after buffering is added, and then equivalent is divided into two, and pipettes into two colorimetric cylinders,
5 μM of mercury ion is added in one of them, measures the absorption spectrum of the two after response 60min respectively.
Occurs apparent absorption peak at 415nm it can be seen that being added after mercury ion, this illustrates that the probe has as colorimetric
Probe realizes the potentiality of the quantitative analysis to mercury ion.
Although with above embodiments describe the present invention, it should be appreciated that before the spirit without departing substantially from the present invention
It puts, the present invention further can be modified and be changed, and these modifications and variation all belong to the scope of protection of the present invention it
It is interior.
Claims (5)
1. compound has following structure
Wherein:R1, R2, R3And R4For independently selected from by hydrogen atom, linear or branched alkyl group, straight or branched alkoxyl, sulfonic acid
The group of base, ester group and hydroxyl composition;And R therein1, R2, R3And R4It can be identical or different.
2. compound according to claim 1, for the compound such as lower structure:
3. the preparation for detecting mercury ion content in sample, it includes the compounds having following structure:
Wherein:R1, R2, R3And R4For independently selected from by hydrogen atom, linear or branched alkyl group, straight or branched alkoxyl, sulfonic acid
The group of base, ester group and hydroxyl composition;And R therein1, R2, R3And R4It can be identical or different.
4. preparation according to claim 3, wherein the compound is:
。
5. preparation according to claim 3, wherein the sample is water sample sample.
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Cited By (1)
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CN110938051A (en) * | 2019-12-19 | 2020-03-31 | 济南大学 | Probe for efficiently detecting mercury ions, preparation method and application |
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Non-Patent Citations (1)
Title |
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QIAO LI ET AL: "A new coumarin-carbonothioate-based turn-on fluorescent chemodosimeter for selective detection of Hg2+", 《INORGANICA CHIMICA ACTA》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110938051A (en) * | 2019-12-19 | 2020-03-31 | 济南大学 | Probe for efficiently detecting mercury ions, preparation method and application |
CN110938051B (en) * | 2019-12-19 | 2022-05-10 | 济南大学 | Probe for efficiently detecting mercury ions, preparation method and application |
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Application publication date: 20180925 |