CN107337640B - Fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe and preparation method and application thereof - Google Patents

Fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe and preparation method and application thereof Download PDF

Info

Publication number
CN107337640B
CN107337640B CN201710610428.1A CN201710610428A CN107337640B CN 107337640 B CN107337640 B CN 107337640B CN 201710610428 A CN201710610428 A CN 201710610428A CN 107337640 B CN107337640 B CN 107337640B
Authority
CN
China
Prior art keywords
formula
fluorescent probe
hydroxyquinoline
compound
fluorene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710610428.1A
Other languages
Chinese (zh)
Other versions
CN107337640A (en
Inventor
霍延平
李宗植
谭继华
王凯
熊靖雯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong University of Technology
Original Assignee
Guangdong University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong University of Technology filed Critical Guangdong University of Technology
Priority to CN201710610428.1A priority Critical patent/CN107337640B/en
Publication of CN107337640A publication Critical patent/CN107337640A/en
Application granted granted Critical
Publication of CN107337640B publication Critical patent/CN107337640B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/24—Oxygen atoms attached in position 8
    • C07D215/26—Alcohols; Ethers thereof
    • 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"
    • 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
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Analytical Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Optics & Photonics (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

The invention provides a fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe and a preparation method and application thereof, and the fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe has a structure shown in a formula (I); the fluorescent probe provided by the invention is applied to Hg2+Detection of Hg only2+Response and strong specificity; for different concentrations of Hg2+Shows good linear relation when detecting, can be applied to Hg2+The quantitative detection of (3); for Hg2+Has high sensitivity for detecting Hg2+Other metal ions have little interference on the measurement result, and the detection method is reliable and stable.

Description

Fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe and preparation method and application thereof
Technical Field
The invention relates to the field of fluorescent probe analysis, in particular to a fluorene modified 8-hydroxyquinoline reaction type fluorescent probe and a preparation method and application thereof.
Background
It is well known that mercury is a heavy metal with serious physiological toxicity, constituting a serious threat to humans and the natural environment in which humans live, whereas Hg is a major factor2+Is the most stable way of existing in various inorganic compounds of mercury, Hg2+Is neither biodegradable nor is it highly susceptible to bioaccumulation, even at very low concentrations, of Hg2+Can also produce considerable toxic effects on human beings, animals and plants through the food chain. Therefore, mercury pollution is still a problem to be solved in a global scale, and real-time and effective detection of Hg is realized2+Can prevent Hg2+The damage of (2).
Most of the existing chemical sensors for detecting mercury ions have some problems in practical application, for example, the existence of various competitive metal ions interferes with the measurement of the mercury ions, the response time is long, and the like, so that the application of the chemical sensors is limited to a certain extent.
Therefore, it is a problem to be solved to provide a method for detecting mercury with a short response time and high detection sensitivity.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe, and a preparation method and application thereof2+Other metal ions than these have little interference with the measurement results.
The invention provides a fluorene modified 8-hydroxyquinoline reaction type fluorescent probe which has a structure shown in a formula (I),
Figure BDA0001358556020000011
the invention also provides a preparation method of the fluorene modified 8-hydroxyquinoline reaction type fluorescent probe, which comprises the following steps:
converting the compound with the structure of the formula (II) into the compound with the structure of the formula (I);
Figure BDA0001358556020000021
preferably, the compound with the structure of formula (II) is prepared according to the following method:
reacting the compound with the structure of the formula (III) with allyl bromide to obtain a compound with the structure of the formula (II),
Figure BDA0001358556020000022
preferably, the catalyst for the reaction is potassium carbonate.
Preferably, the reaction temperature is 60-65 ℃.
Preferably, the compound with the structure of the formula (III) is prepared according to the following method:
mixing the compound with the structure of formula (IV) and pyridine aqueous solution for reaction to obtain a compound with the structure of formula (III);
Figure BDA0001358556020000023
preferably, the reaction temperature is 130-140 ℃.
Preferably, the compound with the structure of formula (IV) is prepared according to the following method:
reacting 8-hydroxyquinaldine, 2-fluorenylformaldehyde and acetic anhydride to obtain the compound with the structure of the formula (IV).
Preferably, the reaction temperature is 135-145 ℃.
The invention also provides a method for detecting Hg2+The fluorescent probe is the fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe;
Figure BDA0001358556020000024
compared with the prior art, the invention provides a fluorene modified 8-hydroxyquinoline reaction type fluorescent probe and a preparation method and application thereof, and the fluorene modified 8-hydroxyquinoline reaction type fluorescent probe has a structure shown in a formula (I); the fluorescent probe provided by the invention is applied to Hg2+Detection, the detection sensitivity is high, and other metal ions have little interference on the detection result; experimental results show that the fluorescent probe provided by the invention only faces Hg2+Response and strong specificity; for different concentrations of Hg2+Shows good linear relation when detecting, can be applied to Hg2+The quantitative detection of (3); for Hg2+Has high sensitivity for detecting Hg2+Other metal ions have little interference on the measurement result, and the detection method is reliable and stable. The technical defects that the detection of mercury ions has long response time and low detection sensitivity in the prior art are overcome.
Drawings
FIG. 1 is a hydrogen spectrum of a fluorene-modified 8-hydroxyquinoline-based reactive fluorescent probe prepared in example 1 of the present invention;
FIG. 2 is a carbon spectrum of a fluorene-modified 8-hydroxyquinoline-based reactive fluorescent probe prepared in example 1 of the present invention;
FIG. 3 shows that the excitation wavelength of the fluorene-modified 8-hydroxyquinoline reactive fluorescent probe prepared in the embodiment of the present invention is 350nm with respect to Hg2+(ii) selective fluorescence measurements;
FIG. 4 is a graph showing the fluorescence intensity and the titration curve of mercury ions of a fluorene-modified 8-hydroxyquinoline-based reactive fluorescent probe prepared in an example of the present invention;
FIG. 5 shows a fluorene-modified 8-hydroxyquinoline-based reactive fluorescent probe and Hg prepared according to an embodiment of the present invention2+A graph showing the relationship between the concentration and the fluorescence intensity of the 8-hydroxyquinoline derivative;
FIG. 6 is a bar graph showing the variation of the fluorescence peak intensity of a fluorene-modified 8-hydroxyquinoline compound before and after different metal ions are added to the fluorene-modified 8-hydroxyquinoline reactive fluorescent probe prepared in the embodiment of the present invention;
FIG. 7 is a graph showing the comparison of fluorescence intensity of a fluorene-modified 8-hydroxyquinoline reaction-type fluorescent probe prepared according to an embodiment of the present invention at different pH values after addition of mercury ions;
FIG. 8 is a diagram of a reaction recognition mechanism of a fluorene-modified 8-hydroxyquinoline-based reactive fluorescent probe and mercury ions prepared in the embodiment of the present invention.
Detailed Description
The invention provides a fluorene modified 8-hydroxyquinoline reaction type fluorescent probe which has a structure shown in a formula (I),
Figure BDA0001358556020000031
the invention also provides a preparation method of the fluorene modified 8-hydroxyquinoline reaction type fluorescent probe, which comprises the following steps:
converting the compound with the structure of the formula (II) into the compound with the structure of the formula (I);
Figure BDA0001358556020000041
according to the invention, the compound with the structure of formula (II) is converted into the compound with the structure of formula (I); specifically, the compound with the structure of formula (II) reacts with N-methyl pyrrolidone to obtain the compound with the structure of formula (I); the feeding ratio of the compound with the structure shown in the formula (II) to N-methylpyrrolidone is preferably 6.0mmol to (8-15) mL, and more preferably 6.0mmol to (10-12) mL; the reaction temperature is preferably 200-220 ℃, more preferably 210-215 ℃, and the reaction time is preferably 3-4 h.
In the invention, the compound with the structure of formula (II) is preferably prepared according to the following method:
reacting the compound with the structure of the formula (III) with allyl bromide to obtain a compound with the structure of the formula (II),
Figure BDA0001358556020000042
specifically, the compound with the structure of formula (III) and allyl bromide are reacted to obtain the compound with the structure of formula (II), wherein the catalyst for the reaction is preferably potassium carbonate; the solvent for the reaction is preferably acetone; the compound of the formula (III), K2CO3The feed ratio of 3-bromopropene to acetone is preferably 8.0 mmol: 12 mmol: (1-1.5) mL: (30-35) m; the reaction temperature is preferably 55-65 ℃; more preferably 60-63 ℃; the reaction time is preferably 3 to 5 hours, and more preferably 4 to 4.5 hours.
In the invention, the compound with the structure of formula (III) is preferably prepared according to the following method:
mixing the compound with the structure of formula (IV) and pyridine aqueous solution for reaction to obtain a compound with the structure of formula (III);
Figure BDA0001358556020000043
specifically, the compound with the structure of formula (IV) and pyridine aqueous solution are mixed and reacted to obtain the compound with the structure of formula (III); wherein the feeding ratio of the compound with the structure of the formula (IV), pyridine and water is preferably 10.0 mmol: 10mL to (5-10) mL; the reaction temperature is preferably 120-140 ℃, and more preferably 130-135 ℃; the reaction time is preferably 3 to 4 hours.
In the invention, the compound with the structure of formula (IV) is preferably prepared according to the following method:
reacting 8-hydroxyquinaldine, 2-fluorenylformaldehyde and acetic anhydride to obtain a compound with a structure shown in a formula (IV); wherein the feeding ratio of the 8-hydroxyquinaldine to the 2-fluorenylformaldehyde to the acetic anhydride is preferably 14.0mmol to (16.0-18.0) mmol to (10-15) mL; the reaction temperature is preferably 130-145 ℃, more preferably 135-140 ℃, and the reaction time is 14-20 hours, more preferably 16-18 hours.
More specifically, the preparation process of the structure of formula (I) of the present invention is as follows:
Figure BDA0001358556020000051
the invention provides a fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe and a preparation method and application thereof, and the fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe has a structure shown in a formula (I); the fluorescent probe provided by the invention is applied to Hg2+Detection of Hg only2+Response and strong specificity; for different concentrations of Hg2+Shows good linear relation when detecting, can be applied to Hg2+The quantitative detection of (3); for Hg2+Has high sensitivity for detecting Hg2+Other metal ions have little interference on the measurement result, and the detection method is reliable and stable. The technical defects that the detection of mercury ions has long response time and low detection sensitivity in the prior art are overcome. The fluorescent probe for detecting mercury ions prepared by the invention is an ideal mercury ion chemical sensor which has the advantages of simple structure, simple synthesis method, high yield, cheap and easily obtained raw materials and easy preparation.
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example is a specific example of the preparation of a fluorescent probe having the structure of formula (I) according to the above preparation method.
14.0mmol of 8-hydroxyquinaldine and 16mmol of 2-fluorenylformaldehyde are dissolved in 10ml of acetic anhydride and mixed, heated and stirred at 135 ℃, condensed and refluxed for 16 hours, and cooled to room temperature. Purifying by column chromatography, eluting with petroleum ether/ethyl acetate, and separating to obtain light brown solid which is compound of formula (IV).
Dissolving 10.0mmol of the compound with the structure of the formula (IV) and 10ml of pyridine, heating and stirring at 130 ℃, adding 5ml of water, stirring and heating, continuing to perform condensation reflux reaction for 4 hours, and cooling to room temperature. Purifying by column chromatography, eluting with petroleum ether/ethyl acetate, and separating to obtain yellow solid, i.e. the compound of formula (III).
8.0mmol of the compound of the formula (III) and 30ml of acetone, 1ml of 3-bromopropene and 12mmol of K2CO3Mixing, heating at 60 deg.C while stirring, reflux-condensing for 4 hr, and cooling to room temperature. Purifying by column chromatography, eluting with petroleum ether/ethyl acetate as eluent, and separating to obtain light yellow solid, i.e. the compound with the structure of formula (II).
6.0mmol of the compound having the structure of formula (II) and 10ml of N-methylpyrrolidone are dissolved, heated and stirred at 210 ℃, condensed and refluxed for reaction for 3 hours, and cooled to room temperature. And (3) purifying by column chromatography, wherein an eluant is petroleum ether/ethyl acetate, and separating to obtain a yellow solid, namely the fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe with the structure of the formula (I).
The obtained fluorescent probe with the structure shown in the formula (I) is detected, and the result is shown in figures 1-2, wherein figure 1 is a hydrogen spectrum of the fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe prepared in the embodiment 1 of the invention; FIG. 2 is a carbon spectrum of a fluorene-modified 8-hydroxyquinoline-based reactive fluorescent probe prepared in example 1 of the present invention.
Example 2
This example is the preparation of C according to the preparation method described above27H21Specific examples of NO.
14.0mmol of 8-hydroxyquinaldine and 17mmol of 2-fluorenylformaldehyde are dissolved in 10ml of acetic anhydride and mixed, heated and stirred at 140 ℃, condensed and refluxed for reaction for 18 hours, and cooled to room temperature. Purifying by column chromatography, eluting with petroleum ether/ethyl acetate, and separating to obtain light brown solid which is compound of formula (IV).
Dissolving 10.0mmol of the compound with the structure of formula (IV) and 10ml of pyridine, heating and stirring at 135 ℃, adding 10ml of water, stirring and heating, condensing and refluxing for 4 hours, and cooling to room temperature. Purifying by column chromatography, eluting with petroleum ether/ethyl acetate, and separating to obtain yellow solid, i.e. the compound of formula (III).
8.0mmol of the compound of the formula (III) and 30ml of acetone, 1ml of 3-bromopropene and 12mmol of K2CO3Mixing, heating and stirring at 65 ℃, condensing and refluxing for 4 hours, and cooling to room temperature. Purifying by column chromatography, eluting with petroleum ether/ethyl acetate as eluent, and separating to obtain light yellow solid, i.e. the compound with the structure of formula (II).
6.0mmol of the compound having the structure of the formula (II) and 10ml of N-methylpyrrolidone are dissolved, heated and stirred at 220 ℃, condensed, refluxed and reacted for 3 hours, and cooled to room temperature. And (3) purifying by column chromatography, wherein an eluant is petroleum ether/ethyl acetate, and separating to obtain a yellow solid, namely the fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe with the structure of the formula (I).
Example 3
This example is the preparation of C according to the preparation method described above27H21Specific examples of NO.
14.0mmol of 8-hydroxyquinaldine and 18mmol of 2-fluorenylformaldehyde are dissolved in 15ml of acetic anhydride and mixed, heated and stirred at 145 ℃, condensed and refluxed for 20 hours, and cooled to room temperature. Purifying by column chromatography, eluting with petroleum ether/ethyl acetate, and separating to obtain light brown solid which is compound of formula (IV).
Dissolving 10.0mmol of the compound with the structure of formula (IV) and 10ml of pyridine, heating and stirring at 140 ℃, adding 5ml of water, stirring and heating, condensing and refluxing for 3 hours, and cooling to room temperature. Purifying by column chromatography, eluting with petroleum ether/ethyl acetate, and separating to obtain yellow solid, i.e. the compound of formula (III).
8.0mmol of the compound of the formula (III) and 35ml of acetone, 1.5ml of 3-bromopropene and 12mmol of K2CO3Mixing, heating and stirring at 65 ℃, condensing and refluxing for 5 hours, and cooling to room temperature. Purifying by column chromatography, eluting with petroleum ether/ethyl acetate as eluent, and separating to obtain light yellow solid, i.e. the compound with the structure of formula (II).
6.0mmol of the compound having the structure of formula (II) and 15ml of N-methylpyrrolidone are dissolved, heated and stirred at 220 ℃, condensed and refluxed for 4 hours, and cooled to room temperature. And (3) purifying by column chromatography, wherein an eluant is petroleum ether/ethyl acetate, and separating to obtain a yellow solid, namely the fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe with the structure of the formula (I).
Example 4
This example shows Hg in the reaction type of fluorene-modified 8-hydroxyquinoline fluorescent probe having the structure of formula (I) prepared in examples 1 to 32+Selectivity of (2).
Adding 10 mu M of fluorene modified 8-hydroxyquinoline reaction type fluorescent probe into a methanol-water mixed solution with the volume ratio of 1: 1, and then respectively adding one equivalent of Li+、Na+、K+、Mg2+、Ca2+、Ba2+、La3+、Fe2+、Fe3+、Co2+、Ni2+、Cu2 +、Ag+、Zn2+、Cd2+、Hg2+And Al3+Measuring the fluorescence spectrum of the system before and after the ion is added by exciting light with the wavelength of 350nm, and obtaining the measurement result as shown in FIG. 3; FIG. 3 shows that the excitation wavelength of the fluorene-modified 8-hydroxyquinoline reactive fluorescent probe prepared in the embodiment of the present invention is 350nm with respect to Hg2+(ii) selective fluorescence measurements; as can be seen from FIG. 3, only Hg was added2+After that, very much appears at 496nmThe strong fluorescence emission peak indicates that the fluorene modified 8-hydroxyquinoline reaction type fluorescent probe provided by the invention is one of the Hg-counter fluorescent probes2+Responsive fluorescence-enhanced probes.
Example 5
Example 1 provides fluorene-modified 8-hydroxyquinoline-based reactive fluorescent probes for different concentrations of Hg2+The fluorescence detection of (3).
Adding 10 μ M fluorene modified 8-hydroxyquinoline reaction type fluorescent probe into methanol-water mixed solution with volume ratio of 1: 1, and adding Hg into the solution according to the concentration of 0 μ M, 1 μ M, 2 μ M, 3 μ M, 4 μ M, 5 μ M, 6 μ M, 7 μ M, 8 μ M, 9 μ M, 10 μ M, 12 μ M, 15 μ M and 20 μ M2+Measuring Hg addition with excitation light having a wavelength of 350nm2+The fluorescence spectra of the 8-hydroxyquinoline-based reaction type fluorescent probe modified with fluorene before and after the reaction type fluorescent probe are shown in FIG. 4. FIG. 4 is a graph showing the fluorescence intensity and the titration curve of mercury ions of the fluorene-modified 8-hydroxyquinoline reactive fluorescent probe prepared in the example of the present invention.
As can be seen from FIG. 4, as Hg flows2+The increase of the ion concentration gradually increases the fluorescence intensity of the fluorene modified 8-hydroxyquinoline reaction type fluorescent probe at 496 nm.
The fluorescence intensity at 496nm was taken as the ordinate, and c (c is Hg)2+Molar concentration) as the abscissa, the working curve is shown in fig. 5, and fig. 5 shows the fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe and Hg prepared according to the embodiment of the present invention2+A graph showing the relationship between the concentration and the fluorescence intensity of the 8-hydroxyquinoline derivative; as can be seen from FIG. 5, Hg2+The fluorescence intensity reaches saturation when the equivalent is 1, and simultaneously, the working curve also clearly shows that the fluorene modifies the 8-hydroxyquinoline reaction type fluorescent probe and Hg2+The binding ratio of (A) to (B) is 1: 1 when Hg is present2+When the concentration range is within 0-10 mu M, the fluorescence intensity at 496nm and c present a good linear relation, and the trend line equation is as follows:
y＝28771.9*c-27858.9，(R＝0.9540)。
the experimental result obtained in the embodiment shows that the fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe can be used for quantitatively detecting Hg2+Intensity of fluorescence thereofAnd the method has good linear relation with c and high sensitivity.
Example 6
Example 1 provides a fluorene-modified 8-hydroxyquinoline-based reactive fluorescent probe for detecting Hg2+Other common metal ions for Hg2+The fluorescence detection of (2) interferes with the experimental determination.
10 mu M of fluorene modified 8-hydroxyquinoline reaction type fluorescent probe is added into a methanol-water mixed solution with the volume ratio of 1: 1, and then one equivalent of Hg is respectively added2+Then, an equimolar amount of Li is added thereto+、Na+、K+、Mg2+、Ca2+、Ba2 +、La3+、Fe2+、Fe3+、Co2+、Ni2+、Cu2+、Ag+、Zn2+、Cd2+、Hg2+And Al3+Ion, exciting light with wavelength of 350nm, measuring Hg added2+The fluorescence spectra of the fluorene-modified 8-hydroxyquinoline-based reactive fluorescent probe before and after the ion, the recorded intensity of fluorescence at 496nm and the change of different metal ions are plotted in a bar chart, and the obtained result is shown in fig. 6. FIG. 6 is a histogram of the change in fluorescence peak intensity of fluorene-modified 8-hydroxyquinoline compounds before and after different metal ions are added to the fluorene-modified 8-hydroxyquinoline reactive fluorescent probe prepared in the example of the present invention.
The result shows that the fluorene modified 8-hydroxyquinoline reaction type fluorescent probe can react with Hg in a methanol-water mixed solution2+The detection of the ions has high sensitivity, the interference of the existence of other metal ions in the solution to the detection result is less, and the detection result is stable and reliable.
Example 7
Example 1 provides a fluorene-modified 8-hydroxyquinoline-based reactive fluorescent probe for detecting Hg2+The fluorescent probe of (1), a contrast experiment of the fluorescent intensity measurement of the probe and the added mercury ions under different pH values.
Adding 10 mu M fluorene modified 8-hydroxyquinoline reaction type fluorescent probe into methanol-water mixed solution with the volume ratio of 1: 1, and then passing through hydrochloric acid (strong acid) and sodium hydroxide (strong base)) Adjusting the pH value of a liquid system to be detected, obtaining solution systems with different pH values within the pH range of 1-12, respectively adding 10 mu M of mercury ions, and measuring the added Hg by using exciting light with the wavelength of 350nm2+The fluorescence change of the fluorene modified 8-hydroxyquinoline reaction type fluorescent probe at 496nm before and after the ion reaction is shown in FIG. 7. FIG. 7 is a graph showing the fluorescence intensity of a fluorene-modified 8-hydroxyquinoline-based reactive fluorescent probe prepared in the example of the present invention after the probe is subjected to different pH values and mercury ions are added.
The result shows that the fluorene modified 8-hydroxyquinoline reaction type fluorescent probe hardly receives the influence of system acid-base change on the detection of mercury ions in a methanol-water mixed solution within the pH range of 4-12, and the probe is suitable for detecting the mercury ions under the physiological pH condition.
In conclusion, the invention provides a fluorene modified 8-hydroxyquinoline reaction type fluorescent probe which has a structure shown in a formula (I); the fluorene modified 8-hydroxyquinoline reaction type fluorescent probe provided by the invention is applied to Hg2+In the detection, only Hg is detected2+Response and strong specificity; the reaction recognition mechanism diagram of the fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe and mercury ions is shown in fig. 8, and fig. 8 is the reaction recognition mechanism diagram of the fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe and mercury ions prepared in the embodiment of the present invention. In addition, the fluorene modified 8-hydroxyquinoline reaction type fluorescent probe provided by the invention can be used for Hg with different concentrations2+Shows good linear relation when detecting, can be applied to Hg2+The quantitative detection of (3); for Hg2+Has high sensitivity for detecting Hg2+Other metal ions have little interference on the measurement result, and the detection method is reliable and stable. The technical defects that the detection of mercury ions has long response time and low detection sensitivity in the prior art are overcome.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (10)

1. A fluorene modified 8-hydroxyquinoline reaction type fluorescent probe has a structure shown in formula (I),
Figure FDA0002351168510000011
2. a preparation method of a fluorene modified 8-hydroxyquinoline reaction type fluorescent probe comprises the following steps:
converting the compound with the structure of the formula (II) into the compound with the structure of the formula (I);
Figure FDA0002351168510000012
3. the method according to claim 2, wherein the compound having the structure of formula (II) is prepared by the following method:
reacting the compound with the structure of the formula (III) with allyl bromide to obtain a compound with the structure of the formula (II),
Figure FDA0002351168510000013
4. the method of claim 3, wherein the catalyst for the reaction is potassium carbonate.
5. The method according to claim 3, wherein the reaction temperature is 60 to 65 ℃.
6. The preparation method according to claim 3, wherein the compound having the structure of formula (III) is prepared by the following method:
mixing the compound with the structure of formula (IV) and pyridine aqueous solution for reaction to obtain a compound with the structure of formula (III);
Figure FDA0002351168510000014
7. the method according to claim 6, wherein the reaction temperature is 130 to 140 ℃.
8. The method of claim 6, wherein the compound of formula (IV) is prepared by the following method:
reacting 8-hydroxyquinaldine, 2-fluorenylformaldehyde and acetic anhydride to obtain the compound with the structure of the formula (IV).
9. The preparation method according to claim 8, wherein the reaction temperature for obtaining the compound having the structure of formula (IV) is 135-145 ℃.
10. Be used for detecting Hg2+The fluorescent probe of (1), which is the fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe of claim 1.
CN201710610428.1A 2017-07-24 2017-07-24 Fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe and preparation method and application thereof Active CN107337640B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710610428.1A CN107337640B (en) 2017-07-24 2017-07-24 Fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710610428.1A CN107337640B (en) 2017-07-24 2017-07-24 Fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN107337640A CN107337640A (en) 2017-11-10
CN107337640B true CN107337640B (en) 2020-04-14

Family

ID=60217485

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710610428.1A Active CN107337640B (en) 2017-07-24 2017-07-24 Fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN107337640B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109180568A (en) * 2018-09-14 2019-01-11 济南大学 A kind of identification mitochondria and fluorescence probe and application with two-phpton property

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104447535A (en) * 2014-11-21 2015-03-25 广东工业大学 Novel dimeric crystal containing fluorene 8-hydroxyquinoline type zinc complex as well as preparation method and application of dimeric crystal
CN106496117A (en) * 2016-10-21 2017-03-15 广东工业大学 A kind of mercury ion Ratiometric fluorescent probe of 8 hydroxyquinoline class and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104447535A (en) * 2014-11-21 2015-03-25 广东工业大学 Novel dimeric crystal containing fluorene 8-hydroxyquinoline type zinc complex as well as preparation method and application of dimeric crystal
CN106496117A (en) * 2016-10-21 2017-03-15 广东工业大学 A kind of mercury ion Ratiometric fluorescent probe of 8 hydroxyquinoline class and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
（E）-2-[2-(4-乙烯氧基苯基)乙烯基]喹啉的合成及其荧光性质的初步研究;张燕华;《西北农林科技大学硕士学位论文》;20160430;全文 *
含吡嗪、喹啉荧光探针的合成及其对金属离子的识别研究;杨海亮,等;《化学试剂》;20100131;第32卷(第1期);1-6 *

Also Published As

Publication number Publication date
CN107337640A (en) 2017-11-10

Similar Documents

Publication Publication Date Title
CN108409726B (en) Coumarin 2-hydrazinobenzothiazole Schiff base Cd2+Preparation and application of fluorescent probe
Tian et al. A novel turn-on Schiff-base fluorescent sensor for aluminum (III) ions in living cells
CN113979998B (en) Aluminum ion detection fluorescent probe based on 1, 8-naphthalimide as matrix and preparation method and application thereof
CN108169189B (en) Ratiometric fluorescent probe responding to sulfur dioxide/sulfite (hydrogen) salt
CN109971465B (en) Multifunctional fluorescent probe with ESIPT (electron fluorescence tomography) and AIE (electron emission tomography) properties and preparation method and application thereof
CN107090002A (en) A kind of response type naphthalimide fluorescence probe for detecting mercury ion and preparation method and application
CN110055056B (en) Benzimidazolyl substituted quinolinone fluorescent probe and preparation method and application thereof
CN110117282A (en) A kind of zinc ion fluorescent compound and the preparation method and application thereof
CN110964515B (en) double-Schiff base aluminum ion fluorescent probe, and synthesis method and application thereof
CN103472047A (en) Fluorescence detection method for amino acid under different pH values
CN107325083B (en) Coumarin fluorophore ratio fluorescent molecular probe for iron ion detection and synthesis and use methods thereof
CN107337640B (en) Fluorene-modified 8-hydroxyquinoline reaction type fluorescent probe and preparation method and application thereof
CN111795960B (en) Molecular platform for detecting different forms of iodine by spectrometry and colorimetry, and preparation method and application thereof
CN105319194A (en) Method for continuously detecting I<-> and Hg<2+> by using aggregation-induced emission type fluorescent sensing molecule
KR101105381B1 (en) Mercury selective fluorescent compound and mercury selective fluorescent chemosensor comprising the same
Lee et al. “Turn-on” fluorescent and colorimetric detection of Zn2+ ions by rhodamine-cinnamaldehyde derivative
CN108558859B (en) Preparation and application of visible long-wave Hg2+ fluorescent probe based on benzopyran
CN107727620B (en) Kit for detecting nitrite ions and application thereof
CN113387839B (en) 2-amino-3- (3-phenyl-allylamino) -2-dinitrile, preparation method and application thereof
CN106496117B (en) A kind of mercury ion Ratiometric fluorescent probe of 8-hydroxyquinoline class and preparation method thereof
CN110317175B (en) Naphthalene derivative and synthesis method and application thereof
CN113234046B (en) Fluorescent probe for detecting hypochlorite ions and application thereof
CN105606607B (en) A kind of preparation method and application than colour pattern mercury ion probe of the organic iridium of cationic (III) complex
CN105384701B (en) A kind of benzotriazole benzaldehyde-p-phenylenediamine bi-schiff base and preparation method thereof
CN110172339B (en) Fluorescent probe and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant