CN101037594A - Fluoride fluorescence probe and special fluorescence compound - Google Patents
Fluoride fluorescence probe and special fluorescence compound Download PDFInfo
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- CN101037594A CN101037594A CN 200610057592 CN200610057592A CN101037594A CN 101037594 A CN101037594 A CN 101037594A CN 200610057592 CN200610057592 CN 200610057592 CN 200610057592 A CN200610057592 A CN 200610057592A CN 101037594 A CN101037594 A CN 101037594A
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Abstract
The invention discloses a fluorinion fluorescent probe and special fluorescent compound for the same. Structure of the provided fluorescent compound is shown in formula I, wherein, n is integer of 1-4, R is fluorescent functional group containing conjugated aromatic rings, and M is potassium or sodium. Advantages of the fluorescent compound are: synthesis is simple , water-solubility is good, complex compound formed with Fe3+ at acid condition can be used for detecting fluorinion, detecting limit is low, detecting sensitivity and selectivity is high.
Description
Technical field
The present invention relates to a kind of fluorion fluorescent probe and special-purpose fluorescent chemicals thereof.
Background technology
Anionic detection occupies very consequence in supramolecular chemistry, wherein the detection of fluorion is particularly important.Because fluorion has a material impact to healthy, as the vital role of fluorion in oral cavity health and osteoporosis.Up to now, existing many seminars design and reported that some fluorescent optical sensors detect fluorion.These fluorescent optical sensors roughly can be divided three classes: a class is to utilize Lewis Acids and Bases to be used for detecting (as utilizing the affinity interaction of boron and fluorion); One class is to utilize to contain thiocarbamide or the unitary fluorescence molecule of urea, and the hydrogen bond action by itself and fluorion detects fluorion; One class is to pass through chemical reaction.But these fluorescent optical sensors have following shortcoming: can not be applied in the aqueous systems; Selectivity is low, serious interference; Can not detect immediately etc., thereby limit their application.Explore for this reason and can realize that to fluorion highly sensitive, highly selective and the instant method that detects seem particularly important at aqueous phase.
In recent years, substitution method is widely used in the design of fluorescent optical sensor molecule.Its principle is fluorescence indication molecule and complexing of metal ion, and its fluorescence strengthens or quencher.Add assay then, assay and complexing of metal ion discharge fluorescence molecule, and system fluorescence recovers.The advantage of this method is: (1) fluorescent probe is simple, and original position generates, and can be applied to water; (2) use fluorescence as detection means, highly sensitive; (3) this method can be come optionally check and analysis thing by the complexation constant of regulation and control fluorescence molecule and metal ion.The characteristics of substitution method detect anionic feasible way for we provide a class.
Summary of the invention
The purpose of this invention is to provide a kind of fluorescent chemicals, fluorescent probe that constitutes by this fluorescent chemicals and preparation method thereof.
Fluorescent chemicals provided by the present invention, structure be suc as formula shown in the I,
(formula I)
Wherein, n is the integer of 1-4, and R is the fluorescent functional group that contains the conjugation aromatic nucleus, and M is potassium or sodium.
Here, R is preferably naphthyl, anthryl or pyrenyl.Preferred, R is an anthryl in formula I structure, and n is 1, and M is a potassium.
The preparation method of this fluorescence molecule comprises the steps:
1) with the sodium hydride be alkali, dimethyl sulfoxide (DMSO) is a solvent, utilizes the Bian Ji chlorine of anthracene and the carboxylic acid ester compound that the diethyl malonate reaction obtains anthracene;
2) carboxylic acid ester compound is reacted with potassium hydroxide in ethanol, obtain described fluorescence molecule.
By the formed fluorescent probe that is used to detect fluorion of fluorescence molecule of the present invention, be the fluorescent chemicals and the Fe of formula I structure
3+The complex compound that forms.
This complex compound can form under acidic conditions, and the inventor confirms that by experiment this probe has good selectivity and sensitivity at aqueous phase to fluorion, and can realize instant detection, is the good fluorescent optical sensor of a class, can be used for detecting fluorion.
Major advantage of the present invention is:
1, the synthetic selected reagent of fluorescent chemicals is all common agents, and synthesis step is simple, target product productive rate height, separate easily, purity height.This method raw material is easy to get, and reaction is simple, and the reaction yield height is fit to a large amount of preparations.
2, fluorescent chemicals has well water-solublely, has thoroughly solved the drawback that can not be applied to pure aquatic system when in the past detecting fluorion.
3, the preparation of fluorescent probe is simple, and consumption is low, and selectivity is good, can get rid of can produce other halide-ionss of interferential to fluorion usually in the past.Detectability is low, can reach every liter of 10 micromole.
Description of drawings
Figure 1A, Figure 1B are 5 * 10
-6When fluorescent chemicals (pH=3.5) the adding mole number that mole is every liter is the iron ion of fluorescence molecule mole number 0.4,0.8,1.0,1.2,1.4,1.6,1.8,2.0, the changing conditions of uv-absorbing;
Fig. 2 is 5 * 10
-6When the fluorescent chemicals (pH=3.5) that mole is every liter adds 0.4,0.8,1.0,1.2,1.4,1.6,1.8,2.0 normal iron ions, the change in fluorescence situation;
Fig. 3 is the linear relationship chart of fluorescence molecule and iron ion complexation constant, wherein F
0Be fluorescent chemicals 5 * 10
-6Mole initial fluorescent value every liter the time;
The variation of ultraviolet when Fig. 4 A, Fig. 4 B are embodiment 2 gained fluorescent probes adding fluorion;
The variation of fluorescence when Fig. 5 is fluorescent probe (pH=3.5) adding fluorion;
When Fig. 6 is fluorescent probe (pH=3.5) fluorion that adds every liter of 0.5 mmole respectively, chlorion, bromide anion, iodide ion, nitrate ion, sulfate ion, perchlorate, acetate ion and benzoate anion ion, the situation of change in fluorescence;
Fig. 7 is containing copper, zinc, nickel, cobalt ion (10 for fluorescent probe
-3Every kind of ion of M/) aqueous phase change in fluorescence situation.
Embodiment
The preparation of embodiment 1, fluorescent chemicals 1 (R is an anthracene, and n=1, M are potassium)
The building-up reactions equation is as follows:
In 30 milliliters of dimethyl sulfoxide (DMSO) (DMSO), add 0.16 gram sodium hydride (60%, 4.16 mmole), stir after 15 minutes, in this suspension liquid, add 1.6 gram diethyl malonates.After the solution becomes clarification, add 9 of 0.4 gram (1.76 mmole), 10-two Bian Ji anthracenes.Then reaction solution was refluxed 5 hours, be cooled to room temperature after, pour in 50 milliliters of frozen water.Filter, the faint yellow filter cake that obtains is purified (leacheate-sherwood oil/1: 9 volume ratio of methylene dichloride) with silica gel column chromatography, and the intermediate product that obtains is a faint yellow solid, productive rate 62.5%.
Mass spectrum (EI): m/z 522
Fusing point: 177 ℃
Nucleus magnetic hydrogen spectrum (
1H-NMR) (300Hz, CDCl
3): δ 8.32 (d, 4H), 7.51 (d, 4H), 4.30 (d, 4H), 4.02 (m, 8H), 3.84 (t, 2H), 1.05 (m, 12H).
In the mixing solutions of 10 ml methanol and the formation of 10 ml waters, add gained intermediate product above 0.45 gram (0.857 mmole), add 0.2 gram potassium hydroxide then.Refluxed 12 hours.Reaction solution is spin-dried for.And with the methanol wash of methylene dichloride and the 3 * 5mL of 20mL, (R is an anthracene, and n=1), productive rate is 95% to obtain 0.46 gram fluorescent chemicals 1.
Mass spectrum (FAB, negative) calculated value 522.9605; Observed value 522.9600
Fusing point:＞300 ℃
Nucleus magnetic hydrogen spectrum
1H-NMR (300Hz, D
2O): δ 8.31 (m, 4H), 7.47 (m, 4I), 4.00 (d, 4H), 3.41 (t, 2H).
The result shows that the products therefrom structure is correct.
The preparation of embodiment 2, fluorescent probe
To 5 * 10
-6In fluorescent chemicals 1 aqueous solution that mole is every liter (pH=3.5), add iron nitrate, Fe
3+With the ratio of the mole number of fluorescent chemicals 1 be 2, fully vibration shakes up, and promptly forms fluorescent probe.
The photophysical property of embodiment 3, fluorescent probe
Figure 1A, Figure 1B are embodiment 1 gained fluorescence molecules (5 * 10
-6M) ultraviolet absorption value is with Fe
3+Variation diagram (the Fe of add-on
3+Add-on is respectively 0.4,0.8,1.0,1.2,1.4,1.6,1.8,2.0 times of fluorescence molecule mole number), Fig. 2 is a gained fluorescence molecule (5 * 10
-6M) fluorescent emission value is with Fe
3+The variation diagram of add-on; Fig. 3 is according to the calculating fluorescence molecule that Fig. 2 did and the linear relationship chart of iron ion complexation constant.Along with the introduction of iron ion, in uv-absorbing figure, the light absorption value that can observe 259 nanometers descends gradually, can observe two isobestic points in 249 nanometers and 265 nanometers, illustrates that fluorescence molecule and iron ion form a stable complex state.Meanwhile, tangible red shift appears in the peak between the 320-450 nanometer.And in fluorescent emission figure, with the adding of iron ion, fluorescence is quencher gradually.The complexation constant scaling system of making in view of the above as shown in Figure 3, the complexation constant of fluorescence molecule and iron is about 4.8 * 10
5
Fig. 4 A, Fig. 4 B are embodiment 2 gained fluorescent probes (5 * 10
-6M) ultraviolet absorption value is with fluorion add-on (F
-Add-on is respectively 4,8,12,16,20,24,28,32 of fluorescent probe molecule mole number, 36,40 times) variation diagram; The variation diagram of fluorescence when Fig. 5 is fluorescent probe (pH=3.5) adding fluorion.Fig. 4 A, Fig. 4 B and Fig. 5 have disclosed the principle of fluorescent probe and fluorine effect.Because fluorion and the strong complexing action of iron ion, when the concentration of fluorion reaches finite concentration, fluorion is fought for out iron ion from fluorescent probe.Thereby make fluorescence molecule dissociate out, solution fluorescence recovers.In ultraviolet and fluorogram, all can observe molecule 1 free process gradually.According to Fig. 5 as can be known, fluorion also is type complexing in 1: 1 to the formed within the specific limits complex compound of the competition coordination of iron.
When Fig. 6 was the fluorion that adds every liter of 0.5 mmole in the fluorescent probe (pH=3.5) respectively, chlorion, bromide anion, iodide ion, nitrate ion, sulfate ion, perchlorate, acetate ion and benzoate anion ion, (1 to 9 pairing ion was respectively fluorion, chlorion, bromide anion, iodide ion, nitrate ion, sulfate ion, perchlorate, acetate ion and benzoate anion ion to the situation of the initial and final change in fluorescence of fluorescence; In every group of data, the former is the initial fluorescence value, and the latter is final fluorescent value).As can be seen from the figure, this fluorescent probe has good selectivity to fluorion.
Fig. 7 is containing copper, zinc, nickel, cobalt ion (10 for fluorescent probe
-3Every kind of ion of M/) aqueous phase change in fluorescence situation.Owing to contain a large amount of transition metal ions, this aqueous systems need be through anticipating before adding probe.The sodium hydroxide that adds 0.1M in the aqueous solution is adjusted to 13 with pH, filtering-depositing.PH with filtrate is adjusted to 3.5 subsequently, adds fluorescent probe, and system fluorescence recovers.In the finite concentration scope, fluorescence intensity and fluorinion concentration are linear.By with Fig. 5 more as can be known, the error of this method is about 9%, is far smaller than SPADNS method (can reach 67%).
In fluorescent probe of the present invention, the R group provides fluorescence source, can select the multiple fluorescent functional group that contains the conjugation aromatic nucleus, as naphthalene, anthracene, pyrene etc.; Carboxylate salt is the complexing group, and the mechanism of action is heavy metal ion and molecular complex quench fluorescence.Compound was synthetic when R was other substituting groups in this compound, and in the time of can being anthryl with reference to R synthetic (embodiment 1) of compound, because the reaction of Bian Ji chlorine and diethyl malonate is classical reaction, similar compound is all synthetic easily.So when R was naphthalene and pyrene, fluorescent probe still had good selectivity to fluorion.
Claims (6)
1, the compound of formula I structure,
Wherein, n is the integer of 1-4, and R is the fluorescent functional group that contains the conjugation aromatic nucleus, and M is potassium or sodium.
2, compound according to claim 1 is characterized in that: described R is naphthyl, anthryl or pyrenyl.
3, compound according to claim 1 is characterized in that: described R is an anthryl, and n is 1, and M is a potassium.
4, the preparation method of the described compound of claim 3 comprises the steps:
1) with the sodium hydride be alkali, dimethyl sulfoxide (DMSO) is a solvent, utilizes the Bian Ji chlorine of anthracene and the carboxylic acid ester compound that the diethyl malonate reaction obtains anthracene;
2) carboxylic acid ester compound is reacted with potassium hydroxide in ethanol, obtain described compound.
5, a kind of fluorescent probe that is used to detect fluorion is the compound and the Fe of the described formula I structure of claim 1
3+The complex compound that forms.
6, the application of the described fluorescent probe of claim 5 in detecting fluorion.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101109708B (en) * | 2007-09-05 | 2010-05-19 | 南开大学 | Novel magnesium ion fluorescent probe and its manufacturing method and application |
| CN103411908A (en) * | 2013-09-02 | 2013-11-27 | 中国科学院合肥物质科学研究院 | Method for detecting halide ions based on mixed water solution of erythrosin B and Ag<+> by utilizing fluorescence enhancement method or colorimetric method |
| CN104845611A (en) * | 2015-04-28 | 2015-08-19 | 中国科学院理化技术研究所 | Novel fluorine ion ratio fluorescent probe and application |
| CN105085581A (en) * | 2015-09-02 | 2015-11-25 | 大连理工大学 | Carboxylate radical bridged binuclear iron-sulfur-cluster fluorescent probe, preparation method and application thereof |
| CN108132235A (en) * | 2018-02-02 | 2018-06-08 | 首都师范大学 | A kind of method of fluorinion concentration in fluoroscopic examination solution |
| CN113651801A (en) * | 2021-07-01 | 2021-11-16 | 长春工业大学 | Fluorescent probe for selectively identifying fluorine ions and preparation method thereof |
| CN114088693A (en) * | 2021-11-16 | 2022-02-25 | 益诺思生物技术南通有限公司 | Simulated radioactivity18F-labeled cold labeling method and kit |
-
2006
- 2006-03-16 CN CN 200610057592 patent/CN101037594A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101109708B (en) * | 2007-09-05 | 2010-05-19 | 南开大学 | Novel magnesium ion fluorescent probe and its manufacturing method and application |
| CN103411908A (en) * | 2013-09-02 | 2013-11-27 | 中国科学院合肥物质科学研究院 | Method for detecting halide ions based on mixed water solution of erythrosin B and Ag<+> by utilizing fluorescence enhancement method or colorimetric method |
| CN103411908B (en) * | 2013-09-02 | 2015-06-03 | 中国科学院合肥物质科学研究院 | Method for detecting halide ions based on mixed water solution of erythrosin B and Ag<+> by utilizing fluorescence enhancement method or colorimetric method |
| CN104845611A (en) * | 2015-04-28 | 2015-08-19 | 中国科学院理化技术研究所 | Novel fluorine ion ratio fluorescent probe and application |
| CN105085581A (en) * | 2015-09-02 | 2015-11-25 | 大连理工大学 | Carboxylate radical bridged binuclear iron-sulfur-cluster fluorescent probe, preparation method and application thereof |
| CN105085581B (en) * | 2015-09-02 | 2017-10-24 | 大连理工大学 | One class carboxylate radical bridged binuclear iron-sulfur cluster fluorescence probe, preparation method and application |
| CN108132235A (en) * | 2018-02-02 | 2018-06-08 | 首都师范大学 | A kind of method of fluorinion concentration in fluoroscopic examination solution |
| CN108132235B (en) * | 2018-02-02 | 2020-10-02 | 首都师范大学 | Method for detecting concentration of fluorine ions in solution by fluorescence |
| CN113651801A (en) * | 2021-07-01 | 2021-11-16 | 长春工业大学 | Fluorescent probe for selectively identifying fluorine ions and preparation method thereof |
| CN114088693A (en) * | 2021-11-16 | 2022-02-25 | 益诺思生物技术南通有限公司 | Simulated radioactivity18F-labeled cold labeling method and kit |
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