CN105439959A - Mercury ion fluorescence probe compound, preparation method and application - Google Patents

Mercury ion fluorescence probe compound, preparation method and application Download PDF

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Publication number
CN105439959A
CN105439959A CN201511031104.XA CN201511031104A CN105439959A CN 105439959 A CN105439959 A CN 105439959A CN 201511031104 A CN201511031104 A CN 201511031104A CN 105439959 A CN105439959 A CN 105439959A
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steps
mercury ion
organic phase
preparation
fluorescence probe
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Inventor
陈卫华
范蓓
贺永恒
尚玉婷
黄亚涛
王淼
李敏敏
卢嘉
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Institute of Food Science and Technology of CAAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C07D235/12—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms

Abstract

The invention discloses a mercury ion fluorescence probe compound, a preparation method and an application and relates to the technical field of analytical chemistry. The chemical formula of the mercury ion fluorescence probe compound is obtained through derivatization with 2-(2'-hydroxyphenyl) benzimidazole serving as a parent structure. The probe has good selectivity for mercury ions, is high in sensitivity and easy to prepare and is an ideal mercury ion sensing molecule.

Description

A kind of mercury ion fluorescence probe compound, preparation method and application
Technical field
The present invention relates to technical field of analytical chemistry, particularly relate to a kind of mercury ion fluorescence probe compound, preparation method and application thereof.
Background technology
Along with human society and industrial development, mercury and mercuric compounds has been widely used in the industrial fields such as metallurgy, electronics, health care.In above-mentioned industrial production, 2000 ~ 3000 tons of mercury in consequent waste, are about had to be disposed in different forms in the middle of environment.Wherein, the mercury of simple substance form is easy to send out, and the mercury vapour of generation is present in air, and human body, by after respiratory system absorption and direct skin contact, can cause the poisoning and nephrotoxicity of neural system, serious harm HUMAN HEALTH; With the mercury ion that inorganic salt form exists, can be converted into the organic mercuries such as methyl mercury under microbial process, organic mercury is easily absorbed by the body, and not easily excretes.The organic mercury of constantly accumulation in hydrocoles body, along with the raising of food chain grade, finally produces a large amount of accumulations, causes human colony's property mercury poisoning in human body.Such as, last century Japan minamata disease outburst, mainly due to the fish of edible Methylmercury pollution Riverfish, cause pregnant woman, fetus, infant's group deformity and sufferer.For this reason, EPA, WHO careless intake to mercury specifies strict standard, and regulation methyl mercury intake is lower than 1.1 μ g (Kgd), and in tap water, inorganic mercury content is lower than 2ppb.So, the mensuration of mercury content in water body and in aquatic Fish is had great importance.
Mainly contain the instrument analytical methods such as atomic absorption/emmission spectrum, inductivity coupled plasma mass spectrometry, electrochemical method in the detection mercury ion method of development and application, aforesaid method needs to rely on complicated sample handling processes, consuming time longer.Therefore, fluorometry is the novel mercury ion detecting method that development in recent years is got up with its highly sensitive, highly selective and the feature that can realize original position real-time follow-up.Such as, rhodamine fluorescence probe (ChenX, NamS, JouM, etal., Org.Lett., 2008,10,5235-5238), combination probe (YoonS, AlbersA, WoogA, the etal. of fluorescein to be parent and crown ether be recognition unit, J.Am.Chem.Soc., 2005,127,16030-16031), Ratiometric fluorescent probe (ZhangX, LiaoY, QianX, Angew.Chem., Int.Ed., 2008,47,8025-8029).
Based on specificity oxymercuration reaction between mercury ion and vinyl with have the fluorescent parent of ESIPT mechanism, this goal of the invention be to develop a kind of structure simple, be easy to preparation, mercury ion is had to the novel fluorescence probe of highly selective and sensitivity.
Summary of the invention
One object of the present invention is to propose that a kind of molecular structure is simple, productive rate is high, mercury ion is had to the mercury ion fluorescence probe compound of good selectivity and susceptibility.
Another object of the present invention is to propose that a kind of technique is simple, raw material is easy to get, the preparation method of mercury ion fluorescence probe compound easy to implement.
Another object of the present invention is the application proposing a kind of mercury ion fluorescence probe compound.
For reaching this object, on the one hand, the present invention is by the following technical solutions:
A kind of mercury ion fluorescence probe compound, its chemical molecular formula is C 15h 12n 2o, molecular structural formula is:
Preferably, described mercury ion fluorescence probe compound, obtains through derivatize for precursor structure with 2-(2 '-hydroxyphenyl) benzimidazole compound.
On the other hand, the present invention is by the following technical solutions:
A preparation method for mercury ion fluorescence probe compound, follows these steps to carry out:
Steps A, 2-(2 '-hydroxyphenyl) benzoglyoxaline is dissolved in DMF solution, then adds salt of wormwood reaction, after purifying, obtain intermediate;
Step B, intermediate steps A prepared are dissolved in dimethyl sulfoxide (DMSO), then add potassium tert.-butoxide and react;
Step C, employing diluted ethyl acetate solution;
Step D, the organic phase obtained with water and saturated aqueous common salt successively washing step C;
Step e, by step D washing after organic phase carry out drying, revolve steaming and purifying after obtain finalization compound.
Preferably, the chemical molecular formula of the described intermediate in steps A is C 15h 13brN 2o,
Molecular structural formula is:
Preferably, described its chemical molecular formula of finalization compound is C 15h 12n 2o, molecular structural formula is:
Preferably, in steps A, under the protection of rare gas element, the organic phase after adding salt of wormwood is stirred thus reacted;
Preferably, stir the organic phase after adding salt of wormwood under the protection of rare gas element thus carry out steps A 2 after reacting, steps A 2 is, in the organic phase obtained, drip ethylene dibromide, then raised temperature reacts;
Preferably, raised temperature is 80 DEG C;
Preferably, the reaction times in steps A 2 is 10 hours;
Preferably, after the reaction in steps A 2 terminates, be cooled to room temperature, carry out steps A 3, steps A 3 is be poured into water by the solution being cooled to room temperature, adds ethyl acetate and extracts;
Preferably, carry out steps A 4 after steps A 3, steps A 4 is, is used to anhydrous Na after the organic phase saturated aqueous common salt flushing that steps A 3 is obtained 2sO 4dry;
Preferably, carry out steps A 5 after steps A 4, steps A 5 obtains described intermediate for revolving to steam and adopt silicagel column to carry out purifying to organic phase dried in steps A 4;
Preferably, the mol ratio of 2-(2 '-hydroxy phenyl) benzoglyoxaline and salt of wormwood is 1:3;
Preferably, the mol ratio of 2-(2 '-hydroxy phenyl) benzoglyoxaline and ethylene dibromide is 1:10.
Preferably, in step B, the mol ratio of intermediate and potassium tert.-butoxide is 1:1.5;
Preferably, in step B, the reaction times is 4 hours.
Preferably, in step e, anhydrous sodium sulphate is adopted to carry out drying to the organic phase after washing in step D.
Preferably, the eluent that in step e, purifying adopts is ethyl acetate and normal hexane, and ratio is 1:1.
Again on the one hand, the present invention is by the following technical solutions:
An application for mercury ion fluorescence probe compound, described mercury ion fluorescence probe is used for mercury content sensing detection in water environment system, and described sensing detection is that fluorescence intensity detects.
Beneficial effect of the present invention is:
Mercury ion fluorescence probe molecular structure of compounds provided by the invention is simple, productive rate is high, other metal ion disturbance abilities good, highly sensitive to mercury ion selectivity, anti-are strong, is a kind of desirable mercury ion sensor molecules.
Preparation method's technique of mercury ion fluorescence probe compound provided by the invention is simple, raw material is easy to get, easy to implement and probe productive rate is high.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of mercury ion fluorescence probe compound provided by the invention.
Fig. 2 is that mercury ion fluorescence probe compound provided by the invention and mercury ion react recognition mechanism schematic diagram;
Fig. 3 is the fluorescence intensity of mercury ion fluorescence probe compound provided by the invention and the titration curve figure of mercury ion.
Embodiment
Technical scheme of the present invention is further illustrated by embodiment below in conjunction with accompanying drawing.
It is the mercury ion fluorescence probe compound that fluorophore (i.e. precursor structure) obtains through derivatize with 2-(2 '-hydroxyphenyl) benzoglyoxaline that the present invention proposes a kind of, and its chemical molecular formula is, molecular structural formula is:
Thus realize the highly selective of mercury ion and the detection of high sensitivity.
Further, present invention also offers the preparation method of above-mentioned mercury ion fluorescence probe compound, as shown in Figure 1, its preparation method specifically follows these steps to carry out:
Steps A 1,2-(2 '-hydroxyphenyl) benzoglyoxaline (0.35mmol) is dissolved in 5mLN, in dinethylformamide solution, then add salt of wormwood (1.05mmol), under the protection of rare gas element, the organic phase after adding salt of wormwood is stirred thus reacted;
Steps A 2, to obtain organic phase in drip ethylene dibromide (3.5mmol), then raised temperature reacts, and raised temperature is preferably 80 DEG C, and the reaction times is 10 hours, reaction terminate after be cooled to room temperature.
Steps A 3, the solution being cooled to room temperature to be poured into water, to add ethyl acetate and extract, preferably extraction three times, each 10mL.
Steps A 4, to steps A 3 obtain organic phase saturated aqueous common salt rinse after use anhydrous Na 2sO 4dry.
Steps A 5, to organic phase dried in steps A 4 revolve steam and adopt silicagel column carry out purifying obtain intermediate, eluent is ethyl acetate: normal hexane (2:1, v/v).
Wherein, the molecular structural formula of 2-(2 '-hydroxyphenyl) benzoglyoxaline is:
The chemical molecular formula of intermediate is C 15h 9nO 4, molecular structural formula is:
Preferably, the mol ratio of 2-(2 '-hydroxy phenyl) benzoglyoxaline and salt of wormwood is the mol ratio of 1:3,2-(2 '-hydroxy phenyl) benzoglyoxaline and ethylene dibromide is 1:10.
Step B, the intermediate (0.2mmol) steps A prepared are dissolved in 2mL dimethyl sulfoxide (DMSO), and then add potassium tert.-butoxide (0.3mmol) in batches, stirred at ambient temperature, reacts, and the reaction times is 4 hours.
After step C, reaction terminate, use diluted ethyl acetate solution.
Step D, the organic phase obtained with water and saturated aqueous common salt successively washing step C.
Step e, by step D washing after organic phase carry out drying, revolve steaming and purifying after obtain finalization compound, preferably, adopt anhydrous sodium sulphate to carry out drying to the organic phase after washing in step D, the eluent that purifying adopts is ethyl acetate and normal hexane, and ratio is 1:1.
Preferably, in step B, the mol ratio of intermediate and potassium tert.-butoxide is 1:1.5.
The chemical molecular formula of finalization compound is C 15h 12n 2o, molecular structural formula is:
Mercury ion fluorescence probe compound provided by the invention, with 2-(2 '-hydroxyphenyl) benzoglyoxaline for fluorescent parent, successively by with 1,2-ethylene dibromide and potassium tert.-butoxide reaction, vinyl-functional is introduced in phenolic hydroxyl group position, both parent molecule fluorescence was closed, can react with mercury ion generation specificity again.By can there is the vinyl-functional that specificity is reacted at the introducing of reaction parent and mercury ion, in testing process, mercury ion and probe generation oxymercuration react, the fluorescent parent that fluorescence has been closed is made again to recover fluorescent characteristic, thus the detection that can realize mercury ion, effectively can avoid the interference of other metal ion.
Mercury ion fluorescence probe compound and mercury ion react recognition mechanism as shown in Figure 2.Concentration 10 μMs phosphoric acid buffer (pH=7.0) and 10 μMs of HgC l2phosphoric acid buffer (pH=7.0) solution reaction, react with the Hg (II) in this solution, can be there is specificity oxymercuration and react in vinyl and mercury ion, generate fluorescent parent 2-(2 '-hydroxyphenyl) benzoglyoxaline with ESIPT effect
Excited state intramolecular proton transfer (excited-stateintramolecularprotontransfer, ESIPT), ESIPT refers to when probe molecule is by after optical excitation, occurs in the Proton-Transfer Reactions between the contiguous proton donor in excited state molecule inside and proton acceptor.After prepared fluorescent probe and mercury ion react, discharge 2-(2 '-hydroxyphenyl) benzoglyoxaline parent molecule, this molecule can under excitation wavelength be 320nm, launch the fluorescence that wavelength is 454nm, achieve and disappear to the process recovered from fluorescence, thus the specific detection to mercury ion can be realized.
This probe application is in Mercury in Water Body ion detection example:
1. prepare different concns mercury ion solution, concentration gradient is followed successively by 10,20,50,100,200 μMs, solvent 10mMHepes buffered soln;
2. 10 μ L probe solution (1mM are measured, DMSO) in 2mL centrifuge tube, add the mercury ion solution of 100 μ L different concns successively, adding 10mMHepes buffered soln to overall solution volume is 2mL, mix, after leaving standstill 30min, measure fluorescence spectrum.Measuring condition: excitation wavelength 320nm, emmission spectrum scope 400-600nm, as shown in Figure 3, as can be seen from the response curve of Fig. 3, fluorescent probe linearly responds mercury ion response curve, can be applied to mercury ion detecting in actual sample.

Claims (10)

1. a mercury ion fluorescence probe compound, is characterized in that, its chemical molecular formula is C 15h 12n 2o, molecular structural formula is:
2. mercury ion fluorescence probe compound according to claim 1, is characterized in that: described mercury ion fluorescence probe compound, obtains through derivatize for precursor structure with 2-(2 '-hydroxyphenyl) benzimidazole compound.
3. a preparation method for mercury ion fluorescence probe compound, is characterized in that, follows these steps to carry out:
Steps A, 2-(2 '-hydroxyphenyl) benzoglyoxaline is dissolved in DMF solution, then adds salt of wormwood reaction, after purifying, obtain intermediate;
Step B, intermediate steps A prepared are dissolved in dimethyl sulfoxide (DMSO), then add potassium tert.-butoxide and react;
Step C, employing diluted ethyl acetate solution;
Step D, the organic phase obtained with water and saturated aqueous common salt successively washing step C;
Step e, by step D washing after organic phase carry out drying, revolve steaming and purifying after obtain finalization compound.
4. preparation method according to claim 3, is characterized in that, the chemical molecular formula of the described intermediate in steps A is C 15h 13brN 2o,
Molecular structural formula is:
5. preparation method according to claim 3, is characterized in that,
Described its chemical molecular formula of finalization compound is C 15h 12n 2o, molecular structural formula is:
6. preparation method according to claim 3, is characterized in that,
In steps A, under the protection of rare gas element, the organic phase after adding salt of wormwood is stirred thus reacted;
Preferably, stir the organic phase after adding salt of wormwood under the protection of rare gas element thus carry out steps A 2 after reacting, steps A 2 is, in the organic phase obtained, drip ethylene dibromide, then raised temperature reacts;
Preferably, raised temperature is 80 DEG C;
Preferably, the reaction times in steps A 2 is 10 hours;
Preferably, after the reaction in steps A 2 terminates, be cooled to room temperature, carry out steps A 3, steps A 3 is be poured into water by the solution being cooled to room temperature, adds ethyl acetate and extracts;
Preferably, carry out steps A 4 after steps A 3, steps A 4 is, is used to anhydrous Na after the organic phase saturated aqueous common salt flushing that steps A 3 is obtained 2sO 4dry;
Preferably, carry out steps A 5 after steps A 4, steps A 5 obtains described intermediate for revolving to steam and adopt silicagel column to carry out purifying to organic phase dried in steps A 4;
Preferably, the mol ratio of 2-(2 '-hydroxy phenyl) benzoglyoxaline and salt of wormwood is 1:3;
Preferably, the mol ratio of 2-(2 '-hydroxy phenyl) benzoglyoxaline and ethylene dibromide is 1:10.
7. preparation method according to claim 3, is characterized in that, in step B, the mol ratio of intermediate and potassium tert.-butoxide is 1:1.5;
Preferably, in step B, the reaction times is 4 hours.
8. preparation method according to claim 3, is characterized in that: in step e, adopts anhydrous sodium sulphate to carry out drying to the organic phase after washing in step D.
9. preparation method according to claim 3, is characterized in that: the eluent that in step e, purifying adopts is ethyl acetate and normal hexane, and ratio is 1:1.
10. an application for mercury ion fluorescence probe compound, is characterized in that, described mercury ion fluorescence probe is used for mercury content sensing detection in water environment system, and described sensing detection is that fluorescence intensity detects.
CN201511031104.XA 2015-12-31 2015-12-31 Mercury ion fluorescence probe compound, preparation method and application Pending CN105439959A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107121415A (en) * 2017-03-29 2017-09-01 广州医科大学 The method of the label-free fluorescence quick detection mercury ion of single step
CN113004206A (en) * 2021-03-11 2021-06-22 齐齐哈尔大学 Naphthalene derivative fluorescent probe and preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
KAZUHIRO AKUTSU等: "Investigation of substitution effect on fluorescence properties of Zn2+-selective ratiometric fluorescent compounds: 2-(2’-hydroxyphenyl)benzimidazole derivatives", 《TALANTA》 *
MITHUN SANTRA等: "A "reactive" ratiometric fluorescent probe for mercury species", 《ORGANIC LETTERS》 *
OSAMA K. ABOU-ZIED: "Spectroscopy of hydroxyphenyl benzazoles in solution and human serum albumin: detecting flexibility, specificity and high affinity of the warfarin drug binding site", 《RSC ADV.》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107121415A (en) * 2017-03-29 2017-09-01 广州医科大学 The method of the label-free fluorescence quick detection mercury ion of single step
CN113004206A (en) * 2021-03-11 2021-06-22 齐齐哈尔大学 Naphthalene derivative fluorescent probe and preparation method and application thereof
CN113004206B (en) * 2021-03-11 2022-06-17 齐齐哈尔大学 Naphthalene derivative fluorescent probe and preparation method and application thereof

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Application publication date: 20160330