CN101648908A - New water-soluble rare-earth organic chelate fluorescent probe and preparation method thereof - Google Patents
New water-soluble rare-earth organic chelate fluorescent probe and preparation method thereof Download PDFInfo
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- CN101648908A CN101648908A CN200910053878A CN200910053878A CN101648908A CN 101648908 A CN101648908 A CN 101648908A CN 200910053878 A CN200910053878 A CN 200910053878A CN 200910053878 A CN200910053878 A CN 200910053878A CN 101648908 A CN101648908 A CN 101648908A
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- tricarboxylic acid
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Abstract
The invention relates to a new water-soluble rare-earth organic chelate fluorescent probe and a preparation method thereof. The rare-earth fluorescent probe is prepared by adopting difunctional organic ligand 2,4,6-pyridine tricarboxylic acid (PTA) to perform coordination reaction separately with SmCl3 and DyCl3 according to the molar ratio of 3:1 in water solution. The labeled probe has the advantage of strong fluorescence intensity, better water-solubility and stability, high possibility for biomolecular labeling, less influence to labeled biomolecules and the like and the fluorescent probecan be widely applied in fields such as labeled immunoassay, nucleic acid determination, disease diagnosis, detections of microorganisms such as bacterias and viruses. In addition, the production process is easy and the raw material cost and the equipment investment are less so that the development of the application aspect of the new water-soluble rare-earth organic chelate fluorescent probe haspractical development value.
Description
Technical field
The invention belongs to fluoroimmunoassay and field of biological detection, be specifically related to a kind of difunctional organic ligand 2,4,6-pyridine tricarboxylic acid, its water-solubility rare-earth fluorescent probe PTA:Sm
3+And PTA:Dy
3+And preparation method thereof.
Technical background
The temporal resolution immuno analytical method is a kind of on-radiation immuno analytical method of being set up by Soini and Kojola etc. phase early 1980s, because of highly sensitive, simple to operate, tracer is stable, "dead" pollution, typical curve linearity range obviously are better than other technology, the most noticeable.Rare earth element is difficult to directly combine with organism as metal ion, therefore needs a kind of sequestrant with bifunctional group on mark, and an end is connected with rare earth ion, and an end is connected with free amino group or the carboxyl of organism.
The rare-earth fluorescent probe mainly is some rare earth element Sm
3+, Eu
3+, Tb
3+, Dy
3+Title complex, under the irradiation of UV-light, can send very strong fluorescence.Rare earth compounding carries out the superiority that immunoassay has as probe mark: (1) exciting light bands of a spectrum broad, help improving excitation energy, and improve the specific activity of marker; (2) emission band is very narrow, helps reducing background, improves resolving power; (3) the Stokes displacement is bigger, helps getting rid of the interference of non-specific fluorescence; (4) fluorescence lifetime is longer, generally at 100～1000 μ s, and the background fluorescence fall time has only 1～10ns, differ 5～6 orders of magnitude, therefore can adopt the temporal resolution detection technique, the delay measurements time, treat to measure behind the background fluorescence complete attenuation, measured is the fluorescence of rare earth organic complex, thereby eliminates the interference of protein background fluorescence; (5) the rare earth marker is more stable, can preserve 1～2 year, has overcome the shortcoming of markers such as isotropic substance, enzyme.
Summary of the invention
One of purpose of the present invention is to provide a kind of difunctional organic ligand 2,4,6-pyridine tricarboxylic acid PTA.
It is a kind of by difunctional organic ligand 2,4 that two of purpose of the present invention is to provide, and 6-pyridine tricarboxylic acid PTA is the water-solubility rare-earth fluorescent probe PTA:Sm as biomarker that part forms
3+And PTA:Dy
3+
Three of purpose of the present invention is to provide the preparation method of above-mentioned two kinds of water-solubility rare-earth fluorescent probes.
For achieving the above object, the present invention adopts following technical scheme:
A kind of difunctional organic ligand 2,4, the 6-pyridine tricarboxylic acid is characterized in that the structural formula of this organic ligand is:
A kind of water-solubility rare-earth fluorescent probe is characterized in that this rare-earth fluorescent probe has following two kinds of structures:
A. the sour sodium binary complex of samarium (III), i.e. Na are closed in three (2,4, the 6-pyridine tricarboxylic acid)
6[Sm (PTA)
3] 18H
2O, concrete structure is:
B. the sour sodium binary complex of dysprosium (III), i.e. Na are closed in three (2,4, the 6-pyridine tricarboxylic acid)
6[Dy (PTA)
3] 18H
2O, concrete structure is:
A kind of method for preparing above-mentioned water-solubility rare-earth fluorescent probe is characterized in that the concrete steps of this method are:
A. 2 is mixed according to a certain volume with deionized water, slowly add excessive oxygenant KMnO under the stirring at room
4, stirring at room 10～15 hours, 40～50 ℃ were stirred 10～15 hours down, filtered while hot, pH=1～2 of filtrate are regulated in hot wash, white solid is separated out, and filters cold water washing, 95 ℃ slowly drip dense HCl down and dissolve until most of white solid, filtered while hot leaves standstill the adularescent solid under 0～5 ℃ and separates out, and has both obtained difunctional organic ligand 2,4, the 6-pyridine tricarboxylic acid;
B. the preparation method of water-solubility rare-earth fluorescent probe: PTA is dissolved in the deionized water with step a gained, slowly drips SmCl
3The aqueous solution or to DyCl
3The aqueous solution; SmCl wherein
3Or DyCl
3With the mol ratio of PTA be 1: 3; Regulator solution pH to 8～9,60 ℃ stirring reaction 8～12 hours filters, leave standstill under the room temperature treat that it separates out after, washing, vacuum-drying, clear crystal, be water-solubility rare-earth fluorescent probe Na
6[Sm (PTA)
3] 18H
2O or Na
6[Dy (PTA)
3] 18H
2O.
The rare-earth fluorescent probe PTA:Sm that the present invention is prepared
3+And PTA:Dy
3+Characteristics be:
A. self has good water-solubility and stability;
B. have very strong fluorescence intensity and bigger fluorescence quantum yield;
C. be easy to biomolecular labeling, and toxicity is little, less to the influence of the biomolecules of institute's mark;
D. preparation technology is simple, and cost is low, not with an organic solvent, can not pollute environment.
Because this label probe has very strong fluorescence intensity, better water solubility and stability, is easy to biomolecular labeling, to advantages such as the influence of the biomolecules of institute's mark are little, can be widely used in the detection of labelled immune analysis, nucleic acid determination, medical diagnosis on disease, bacterium, virus, microorganism etc., because simple, the raw materials used cost of its preparation technology is low and facility investment is few, therefore has practical significance again aspect its range of application of expansion in addition.
Description of drawings
Fig. 1 is Na
6[Sm (PTA)
3] 18H
2O and Na
6[Dy (PTA)
3] 18H
2Excitation spectrum and the emmission spectrum of O under solid state, wherein (a) is Na
6[Dy (PTA)
3] 18H
2The excitation spectrum of O and emmission spectrum (b) are Na
6[Sm (PTA)
3] 18H
2The excitation spectrum of O and emmission spectrum (5300PC, highly sensitive, Na
6[Dy (PTA)
3] excite and launch slit and be 1.5nm, Na
6[Sm (PTA)
3] excite and launch slit be respectively 3nm and 1.5nm).
Fig. 2 is Na
6[Sm (PTA)
3] and Na
6[Dy (PTA)
3] (concentration is 1.0 * 10 at aqueous solution state
-4Mol/L) excitation spectrum under and emmission spectrum, wherein (a) is Na
6[Dy (PTA)
3] 18H
2The excitation spectrum of O and emmission spectrum (b) are Na
6[Sm (PTA)
3] 18H
2The excitation spectrum of O and emmission spectrum (5300PC, highly sensitive, Na
6[Sm (PTA)
3] the exciting and launch slit and be respectively 10nm and 5nm, Na of solution
6[Dy (PTA)
3] solution excite and launch slit be 3nm).
Embodiment
Below the invention will be further described with example, but be not limited thereto.
Embodiment one: difunctional organic ligand 2,4, the concrete preparation method of 6-pyridine tricarboxylic acid (PTA) is as follows:
With 2 (purity is 99.99%) and KMnO
4(A.R.) be raw material, 2 and deionized water were mixed in 1: 20 by volume, slowly add an amount of KMnO under the stirring at room
4, stirring at room 10～15h afterwards, 40～50 ℃ are stirred 10～15h down, filtered while hot, hot wash three times, filtrate transfers to pH=1 with dense HCl, and white solid is separated out, filter, cold water washing three times, 95 ℃ slowly drip dense HCl down and dissolve filtered while hot until most of white solid, leave standstill adularescent solid (PTA) under 0～5 ℃ and separate out, get two hydration target products.Productive rate 54.5%, m.p.232.8 ℃ (decomposition), the structure of this compound is:
Ultimate analysis: C
8H
5NO
6, experimental value (theoretical value) C:38.62 (38.88), N:5.64 (5.67), H:3.65 (3.67), C/N:6.85 (6.86) .IR (KBr)/cm
-1: 3501.8 (v
COO-H), 3157.7 (v
C-H), 1729.6 (v
C=O), 1701.7 (v
C=O), 1614.9 (v
C=N, in Py), 1568.6 (v
C=C,, in Py).
1H-NMR (DMSO, δ/ppm): 8.52 (s, 2H, py).
Embodiment two: Na
6[Sm (PTA)
3] 18H
2The concrete preparation method of O is as follows:
1.2mmol PTA is dissolved in the small amount of deionized water, treats that solid all after the dissolving, adds deionized water and makes the system cumulative volume reach 50mL.Then with 2.0mL (0.4mmol) SmCl
3The aqueous solution slowly joins in the above-mentioned PTA solution, uses 1.0molL
-1The NaOH aqueous solution transfers to pH about 8, and 60 ℃ of stirring in water bath 8 hours leave standstill a couple of days to separate out clear crystal Na under the room temperature
6[Sm (PTA)
3] 18H
2O, productive rate 60%.
Ultimate analysis: SmNa
6C
24H
42N
3O
36(Na
6[Sm (PTA)
3] 18H
2O), experimental value (theoretical value) C:23.2 (23.31), N:3.26 (3.40), H:3.34 (3.42), C/N 7.12 (6.86) .IR (KBr)/cm
-1: 3452.0 (v
COO-H), 1633.3 (v
C=O), 1558.9 (v
C=N, in Py), 1437.4 (v
C=C, in Py), 1374.6 (v
C=O), 463.3 (v
Sm-O).
Embodiment three: Na
6[Dy (PTA)
3] 18H
2The concrete preparation method of O is as follows:
Na among this preparation method and the embodiment two
6[Sm (PTA)
3] 18H
2The preparation method of O is basic identical, and different is: with the SmCl among the embodiment two
3The aqueous solution changes DyCl into
3The aqueous solution.
Ultimate analysis: DyNa
6C
24H
42N
3O
36(Na
6[Dy (PTA)
3] 18H
2O), experimental value (theoretical value) C 22.43 (23.08), H 3.09 (3.39), and N 3.35 (3.36), C/N 6.70 (6.86) .IR (KBr)/cm
-1: 3441.8 (v
COO-H), 1628.7 (v
As, COO-), 1367.4 (v
S, COO-), 1558.8 (v
C=N, in Py), 1437.5 (v
C=C, in Py), 539.7 (v
Dy-O)
Fig. 1 is Na
6[Sm (PTA)
3] 18H
2O and Na
6[Dy (PTA)
3] 18H
2Excitation spectrum and emmission spectrum (5300PC, highly sensitive, the Na of O under solid state
6[Dy (PTA)
3] excite and launch slit and be 1.5nm, Na
6[Sm (PTA)
3] excite and launch slit be respectively 3nm and 1.5nm).Fig. 2 is Na
6[Sm (PTA)
3] and Na
6[Dy (PTA)
3] (concentration is 1.0 * 10 at aqueous solution state
-4Mol/L) excitation spectrum under and emmission spectrum (5300PC, highly sensitive, Na
6[Sm (PTA)
3] the exciting and launch slit and be respectively 10nm and 5nm, Na of solution
6[Dy (PTA)
3] solution excite and launch slit be 3nm).As can be seen from the figure: this probe exciting light bands of a spectrum broad, help improving excitation energy, improve the specific activity of marker; Emission band is very narrow, helps reducing background, improves resolving power; In dilute aqueous soln, still have very strong fluorescence intensity, and soluble in water, can stable existence in the aqueous solution, be expected to be widely used in the fields such as detection of labelled immune analysis, nucleic acid determination, medical diagnosis on disease, bacterium, virus, microorganism.
Claims (3)
1. difunctional organic ligand 2,4, the 6-pyridine tricarboxylic acid is characterized in that the structural formula of this organic ligand is:
2. a water-solubility rare-earth fluorescent probe adopts difunctional organic ligand 2,4 according to claim 1, and the 6-pyridine tricarboxylic acid is a part, it is characterized in that this rare-earth fluorescent probe has following two kinds of structures:
A. the sour sodium binary complex of samarium (III), i.e. Na are closed in three (2,4, the 6-pyridine tricarboxylic acid)
6[Sm (PTA)
3] 18H
2O, concrete structure is:
B. the sour sodium binary complex of dysprosium (III), i.e. Na are closed in three (2,4, the 6-pyridine tricarboxylic acid)
6[Dy (PTA)
3] 18H
2O, concrete structure is:
3. method for preparing water-solubility rare-earth fluorescent probe according to claim 2 is characterized in that the concrete steps of this method are:
A. 2 is mixed according to a certain volume with deionized water, slowly add excessive oxygenant KMnO under the stirring at room
4, stirring at room 10～15 hours, 40～50 ℃ were stirred 10～15 hours down, filtered while hot, pH=1～2 of filtrate are regulated in hot wash, white solid is separated out, and filters cold water washing, 95 ℃ slowly drip dense HCl down and dissolve until most of white solid, filtered while hot leaves standstill the adularescent solid under 0～5 ℃ and separates out, and has both obtained difunctional organic ligand 2,4, the 6-pyridine tricarboxylic acid;
B. the preparation method of water-solubility rare-earth fluorescent probe: PTA is dissolved in the deionized water with step a gained, slowly drips SmCl
3The aqueous solution or to DyCl
3The aqueous solution; SmCl wherein
3Or DyCl
3With the mol ratio of PTA be 1: 3; Regulator solution pH to 8～9,60 ℃ stirring reaction 8～12 hours filters, leave standstill under the room temperature treat that it separates out after, washing, vacuum-drying, clear crystal, be water-solubility rare-earth fluorescent probe Na
6[Sm (PTA)
3] 18H
2O or Na
6[Dy (PTA)
3] 18H
2O.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070517A (en) * | 2011-01-30 | 2011-05-25 | 天津大学 | 6-methyl-2,3,5-pyridine tricarboxylic acid and synthetic method thereof |
| CN107417710A (en) * | 2017-08-04 | 2017-12-01 | 浙江大学 | A kind of heterocycle metal-organic framework material for high efficiency selected separation absorption and preparation method thereof |
| CN115326770A (en) * | 2022-09-01 | 2022-11-11 | 福州大学 | Time-resolved fluorescent rare earth probe with renal clearance function and preparation method thereof |
-
2009
- 2009-06-26 CN CN200910053878A patent/CN101648908A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070517A (en) * | 2011-01-30 | 2011-05-25 | 天津大学 | 6-methyl-2,3,5-pyridine tricarboxylic acid and synthetic method thereof |
| CN107417710A (en) * | 2017-08-04 | 2017-12-01 | 浙江大学 | A kind of heterocycle metal-organic framework material for high efficiency selected separation absorption and preparation method thereof |
| CN107417710B (en) * | 2017-08-04 | 2019-04-23 | 浙江大学 | A kind of heterocycle metal-organic framework material and preparation method thereof for high efficiency selected separation absorption |
| CN115326770A (en) * | 2022-09-01 | 2022-11-11 | 福州大学 | Time-resolved fluorescent rare earth probe with renal clearance function and preparation method thereof |
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Open date: 20100217 |