LU501538B1 - FLUORESCENT DYE CAPABLE OF DYNAMICALLY MONITORING Fe3+ IN WATER AND APPLICATION THEREOF - Google Patents
FLUORESCENT DYE CAPABLE OF DYNAMICALLY MONITORING Fe3+ IN WATER AND APPLICATION THEREOF Download PDFInfo
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- LU501538B1 LU501538B1 LU501538A LU501538A LU501538B1 LU 501538 B1 LU501538 B1 LU 501538B1 LU 501538 A LU501538 A LU 501538A LU 501538 A LU501538 A LU 501538A LU 501538 B1 LU501538 B1 LU 501538B1
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- fluorescent dye
- fluorene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B55/00—Azomethine dyes
- C09B55/002—Monoazomethine dyes
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- 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
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- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
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- 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
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- 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
- C09K2211/1011—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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
Abstract
Provided in the present invention is a fluorescent dye capable of dynamically monitoring Fe3+ in water and application thereof, which relate to the technical field of organic dye detection functions. The fluorene fluorescent dye provided by the present invention is prepared by taking benzaldehyde and 2- aminofluorene as reaction raw materials by means of a one-step polymerization reaction in a high yield manner. Since an imino group in a fluorene fluorescent dye molecule is not only a conjugated bridging group of fluorene and a phenyl group, but also a site for metal ion complexation, after the imino group is complexed with Fe3+, a sensitive ?off-on-off? double-conversion fluorescence detection signal is caused and has a function of quantitative and qualitative detection on Fe3+; and a method for preparing an imino group has the advantages of mild reaction conditions, simple preparation process, low raw material price, easy implementation, etc., is suitable for industrial popularization, and creates favorable conditions for popularization and application of the fluorene fluorescent dye molecule.
Description
FLUORESCENT DYE CAPABLE OF DYNAMICALLY MONITORING Fe**IN 10501538
[01] The present invention relates to the technical field of organic dye detection functions, and in particular to a fluorene fluorescent dye molecule with a sensitive “off-on-off” fluorescence detection signal on Fe” and application thereof.
[02] Metal ions have been widely applied in industrial production. However, after being discharged into nature along with industrial wastewater in the form of cations, metal ions can seriously contaminate the entire water system, posing serious harms to the ecological system and human living environment. Particularly, metal ions discharged into the ecological environment are difficult to degrade, and are easy to enrich and expand in the biological chain, once people intake water and food contaminated by metal ions, metal ions can be accumulated in the human body, thereby seriously threatening human health. Therefore, it is of vital importance to detect metal ions. For example, iron is the most abundant transition metal in the human body featuring a variety of biological functions. However, excessive iron ions in the body will result in abnormal liver function, myocardial damage, etc. In addition, the content of iron is further related to some neurogenic diseases such as Parkinson's disease and Alzheimer's disease. Therefore, currently, the method for detecting iron ions, featuring rapid development, easy operation and real-time performance, has become a hot spot competitively researched in the fields of chemistry, biological environment, medicine, etc.
[03] In a number of methods for analyzing and detecting iron ions, the fluorescence monitoring technology features advantages of simplicity, rapidity, real-time monitoring, high sensitivity and capability to break through the detection limit of traditional analytical instruments, thereby drawing increasing attention. Iron ions can be detected at the molecular level based on the spectral information generated by selective binding of fluorescence molecular probes to iron ions. The method features simplicity, sensitiveness, accuracy, rapidness and low cost. So far, though a number of reports are available on fluorescent probes for Fe””, most of the reported fluorescence molecular probes for Fe” are changed along with the concentration of the Fe”, and the fluorescence intensity signal is only increased or decreased on an individual basis, while few reports have been published on sensitive molecular probes having fluorescence signals presenting “off-on-off” bidirectional change along with the change of the concentration of Fe”. However, in practices of ordinary people, there are increasingly great demands for dynamic detection on changes in the concentration of Fe”*. Therefore, the development of the fluorescence molecular probe, featuring sensitiveness, easy preparation and dynamic detection of Fe’™, is an urgent demand in various monitoring fields at present.
[04] In the construction of the fluorescence molecular probe, the rigid conjugated fluorene group features the characteristics of high photostability, easy structure 1 modification, etc. and therefore is an excellent fluorescence signal group. The imine LU501538 group with easy synthetization performance features strong metal coordination capability, the complexation selectivity of the imino group to metal ions can be increased by introducing the imine group into fluorescent molecules; and the p-n conjugation upon the connection of the imine group to fluorophore can increase the conjugation of fluorescent molecules. When nitrogen atoms in the imine group coordinate with metal ions, the conjugation degree of fluorescent molecules may be changed, such that fluorescent molecules present sensitive spectral signal changes. Upon combination of the fluorene group with the imine group, a series of fluorescence molecular probes with different recognition properties have been prepared [Q. Xu, X. Wang, G Xing, Y. Zhang, RSC Adv, 2013, 3, 15834-15841; F. Wang, C. Li, X. Zhang, A. Wang, L. Zhou, C. Jia, J. Xu, Y. Chen, Dyes and Pigments, 2019, 171, 107667]. However, the iminofluorene fluorescent dye with a sensitive "off-on-off" fluorescence detection signal on Fe’ has not been reported.
[05] The technical objective of the present invention is to provide a fluorene fluorescent dye molecule featuring a sensitive “off-on-off” fluorescence detection signal on Fe” in water.
[06] Another technical objective of the present invention is to provide a method capable of dynamically monitoring Fe” in working and domestic water for people. The method has the advantages of rapidness, sensitiveness, easy operation, low cost, capability of qualitative and quantitative detection, etc.
[07] In order to achieve the above objectives, the present invention uses the following technical solution:
[08] A molecular structure of a fluorene fluorescent dye capable of dynamically monitoring Fe’ in water:
[10] A method for preparing a fluorene fluorescent dye capable of dynamically monitoring Fe’ in water is as follows:
[11] putting a mmol of benzaldehyde into a round-bottom flask containing B mL of absolute ethyl alcohol, and rising a temperature to reflux; then adding y mmol of 2-aminofluorene and sequentially reacting for 3-5 hours; and filtering a mixture obtained by a reaction, washing same with absolute ethyl alcohol, and drying same to obtain a yellow-brown fluorene fluorescent dye, where a: B: y is 1:15:1.
[12] A preparation reaction formula of the fluorene fluorescent dye capable of dynamically detecting Fe” in water is as follows: 2
- ROH # NHa | Reflex ry
[13] ae
[14] The present invention has the following technical effects that the fluorene fluorescent dye contains an imine bridging group sensitive to metal ions, and after the imine bridging group is complexed with Fe”, a sensitive spectral signal is generated; along with continuous increase of concentration of Fe” in an aqueous solution, maximum fluorescence emission of the dye molecule at 370 nm is obviously enhanced and then reduced, and a sensitive “off-on-off” double-conversion fluorescence detection signal is presented, and features sensitive quantitative detection performance on Fe”; and a preparation process of the fluorene fluorescent dye provided by the present invention has the advantages of low raw material price, simple preparation process, mild reaction conditions, high yield, etc, making it suitable for industrial implementation, and creating favorable conditions for the generalization and application of the fluorene fluorescent dye.
[15] FIG 1 is a nuclear magnetic hydrogen spectrum of a compound obtained in embodiments 1 and 2.
[16] FIG 2 is a fluorescence emission spectrum of a fluorene fluorescent dye after adding different metal ions in 5% methanol aqueous solution.
[17] FIG 3 1s an ultraviolet absorption spectrum of a fluorene fluorescent dye after adding different metal ions in 5% methanol aqueous solution.
[18] FIG 4 is a fluorescence emission spectrum of a fluorene fluorescent dye after adding Fe’" with different concentrations in 5% methanol aqueous solution.
[19] A molecular structure of a fluorene fluorescent dye capable of dynamically monitoring Fe" in water disclosed in the present invention is: # | |
[20] ; and
[21] the fluorene fluorescent dye may be prepared by taking benzaldehyde and 2-aminofluorene as reaction raw materials by means of a one-step polymerization reaction, and a preparation reaction formula is: 3 se © EEE / (D NH, | Reflux COCO
[22]
[23] Example 1
[24] 1 mmol of benzaldehyde was put into a round-bottom flask containing 15 mL of absolute ethyl alcohol, and then a temperature was raised to reflux; then 1 mmol of 2-aminofluorene was added, and sequentially reacting for 3 hours; and a mixture obtained by a reaction was filtered, washed with absolute ethyl alcohol, and dried to obtain a yellow-brown fluorene fluorescent dye A, which has 216 mg and a yield of 80%.
[25] Example 2
[26] 1 mmol of benzaldehyde was put into a round-bottom flask containing 15 mL of absolute ethyl alcohol, and then a temperature was raised to reflux; then 1 mmol of 2-aminofluorene was added, and sequentially reacting for 5 hours; and a mixture obtained by a reaction was filtered, washed with absolute ethyl alcohol, and dried to obtain a yellow-brown fluorene fluorescent dye B, which had 417 mg and a yield of
80.3%.
[27] The compounds A and B obtained in Examples 1 and 2 respectively were analyzed and determined, and nuclear magnetic hydrogen spectra of the both compounds were consistent, and data were as follows: in 'H NMR (CDCl, 400 MHz), 8 8.51 (s, 1H), 7.81 (t, 2H, J = 15.2 Hz), 7.56 (t, 2H, J = 7.2 Hz), 7.48 (s, 1H), 7.42 (d, 2H, J = 4 Hz), 7.36 (d, 2H, J = 3.6 Hz,), 7.32 (d, IH, J = 16 Hz), 7.28 (m, 2H, J = 8 Hz),
6.99 (d, 1H, J = 7.2 Hz ), 3.94 (s, 2H), which were basically consistent with theoretical values of a fluorene fluorescent dye molecular. It may be confirmed therefrom that molecular structures of the compounds A and B were: Où
[28] 4 (J , Le. fluorene fluorescent dye molecule.
[29] Example 3
[30] Fluorescence detection performance of a fluorene fluorescent dye on different metal ions in a 5% methanol aqueous solution was as follows: in the 5% methanol aqueous solution, the fluorene fluorescent dye having a concentration of 2x10” mol/L has a weak fluorescence emission peak near 370 nm; after 10 times of Fe’ were added, maximum fluorescence emission of the fluorene fluorescent dye at 370 nm was quenched; and after other metal ions of Li”, Na”, K”, Ba”, Ca”, Mg”, Co”, Hg”, Mn”, Ni”, Cd”, Zn”, etc. were added, the maximum fluorescence emission of the compound at 370 nm was changed little, which indicated that the fluorene fluorescent dye had a unique fluorescence detection response to Fe”. 4
[31] Example 4 LU501538
[32] Ultraviolet absorption detection performance of a fluorene fluorescent dye on different metal ions in a 5% methanol aqueous solution was as follows: in the 5% methanol aqueous solution, the fluorene fluorescent dye having a concentration of 2x10” mol/L have two absorption shoulder peaks at 340 nm and 274 nm; after 10 times of Fe’ were added, an absorption peak of the fluorene fluorescent dye at 340 nm was shifted red to 366 nm, and an absorption peak of the fluorene fluorescent dye at 274 nm was shifted blue to 251 nm; and after other metal ions of Li", Na”, K*, Ba”, Ca”, Mg”, Co”, He”, Mn”, Ni”, Cd’, Zn”, etc. were added, an ultraviolet absorption spectrum of the compound was hardly changed, which indicated that the fluorene fluorescent dye had both ultraviolet absorption and fluorescence detection responses to Fe”.
[33] Example 5
[34] Fluorescence detection performance of a fluorene fluorescent dye on different concentrations of Fe’ in a 5% methanol aqueous solution was as follows: different concentrations of Fe” were added into the 5% methanol aqueous solution of the fluorene fluorescent dye having a concentration of 2x10” mol/L, and a molar equivalent ratio of the fluorene fluorescent dye to Fe” was 1:0, 1:0.2, 1:0.4, 1:0.6, 1:0.8, 1:1.0, 1:12, 1:14, 1:16, 1:18, 1:2.0, 1:25, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 and 1:10 respectively. Fluorescence emission spectrum data showed that along with continuous increase of the concentration of Fe** in the solution, when the concentration of Fe** was increased from O to 0.6 times, maximum fluorescence emission of the fluorene fluorescent dye near 370 nm was significantly increased to 9.8 times; and when the concentration of Fe”” was increased from 0.6 to 7 times, strong fluorescence emission of the fluorene fluorescent dye was quenched; and when the concentration of Fe” continues being increased and was even increased to 10 times, fluorescence emission of the fluorene fluorescent dye was almost unchanged, which indicated that the fluorene fluorescent dye had potential of dynamic "off-on-off" double-conversion fluorescence signal detection on different concentrations of Fe” in the 5% methanol aqueous solution.
[35] Example 6
[36] Ultraviolet and fluorescence performance of different metal ions in a 5% methanol aqueous solution was as follows: after metal ions of Li”, Na, K”, Ba”, Ca”, Mg”, Co”, He”, Mn”, Ni”, Cd”, Zn”, AI”, Fe”, etc. were added into a mixed solvent in which a volume ratio of methanol to water was 95:5, a fluorescence emission spectrum of a fluorene fluorescent dye was not changed.
Claims (2)
1. A fluorescent dye capable of dynamically monitoring Fe” in water and application, a molecular structure of which is: # |
2. The application of the fluorescent dye capable of dynamically monitoring Fe” in water of claim 1, wherein an imino group in a dye molecule is not only a conjugated bridging group of fluorene and a phenyl group, but also a site for metal ion complexation, and after the imine group is complexed with Fe”*, a sensitive “off-on-off” double-conversion fluorescence detection signal is caused and has a function of quantitative and qualitative detection on Fe’.
1
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111459325.2A CN114105816A (en) | 2021-12-02 | 2021-12-02 | Fe in dynamic monitoring water3+Fluorescent dye and application thereof |
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| Publication Number | Publication Date |
|---|---|
| LU501538B1 true LU501538B1 (en) | 2022-08-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| LU501538A LU501538B1 (en) | 2021-12-02 | 2022-02-23 | FLUORESCENT DYE CAPABLE OF DYNAMICALLY MONITORING Fe3+ IN WATER AND APPLICATION THEREOF |
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|---|---|
| CN (1) | CN114105816A (en) |
| LU (1) | LU501538B1 (en) |
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2021
- 2021-12-02 CN CN202111459325.2A patent/CN114105816A/en not_active Withdrawn
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- 2022-02-23 LU LU501538A patent/LU501538B1/en active IP Right Grant
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