CN101445480A - Bifunctional organic ligand 2, 4, 6-pyridine tricarboxylic acid, water-soluble rare-earth fluorescence labeling material and preparation method thereof - Google Patents
Bifunctional organic ligand 2, 4, 6-pyridine tricarboxylic acid, water-soluble rare-earth fluorescence labeling material and preparation method thereof Download PDFInfo
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- CN101445480A CN101445480A CNA2009100448125A CN200910044812A CN101445480A CN 101445480 A CN101445480 A CN 101445480A CN A2009100448125 A CNA2009100448125 A CN A2009100448125A CN 200910044812 A CN200910044812 A CN 200910044812A CN 101445480 A CN101445480 A CN 101445480A
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Abstract
The present invention relates to two new rare-earth fluorescence labeling materials PTA:Eu<SUP>3+</SUP> and PTA:Tb<SUP>3+</SUP> and preparation method thereof, wherein the rare-earth fluorescence labeling material is prepared by respective coordination reaction between bifunctional organic ligand 2, 4, 6-pyridine tricarboxylic acid (PTA) and EuCl<SUB>3</SUB> and TbCl<SUB>3</SUB> in aqueous medium at molar ratio 3:1. The labeling material is provided with actual meaning in expanding application range because of the simple preparation process, low cost of raw material, and little equipment investment. In addition, because of advantages like strong fluorescence intensity, good water-solubility and stability, easy bimolecular labeling, little influence to labeled bimolecular etc., the invention can be applied for labeling immune analyze, nucleic acid measuring, disease diagnose, detection of bacilli, virus and micro-organisms etc.
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-soluble rare-earth fluorescence labeling material and preparation method thereof.
Technical background
The time resolved fluorescence Measurement for Biotechnique of setting up based on rare-earth fluorescence labeling material long lifetime fluorescent characteristics is through 20 years of development, become one of sensitive Measurement for Biotechnique now, present vigorous growth situation, be widely used in the detection of labelled immune analysis, nucleic acid determination, medical diagnosis on disease, bacterium, virus, microorganism etc.And one of core technology of time resolved fluorescence Measurement for Biotechnique is exactly the exploitation as the rare-earth fluorescence labeling material of biomolecular labeling, have only and constantly develop novel rare-earth fluorescence labeling material, could constantly improve and improve the time resolved fluorescence Measurement for Biotechnique.
But because the high complexity of biological sample, the rare-earth fluorescence labeling material that mark is used often has very high requirement, for example bigger fluorescence quantum yield and molar absorptivity, self has good water-solubility, stability, synthetic easy, be easy to biomolecular labeling, as far as possible little etc. to the influence of the biomolecules of institute's mark.Therefore the design and the preparation of novel rare-earth fluorescence labeling material are very challenging research work, it is not only follow-up biomolecular labeling and carries out the basis of time resolved fluorescence high-sensitivity detection, also is the key that improves, improves and improve the time resolved fluorescence Measurement for Biotechnique.
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.
Two of purpose of the present invention is to provide the preparation method of this organic ligand.
Three of purpose of the present invention is to provide this organic ligand and rare earth metal Eu
3+And Tb
3+Two kinds of rare-earth fluorescence labeling material PTA:Eu that form
3+And PTA:Tb
3+
Three of purpose of the present invention is the preparation method that this provides rare-earth fluorescence labeling material.
For achieving the above object, the present invention adopts following technical scheme to be:
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 ofly prepare above-mentioned difunctional organic ligand 2,4, the method for 6-pyridine tricarboxylic acid is characterized in that the concrete steps of this method are: 2 is dissolved in the deionized water, slowly adds oxygenant KMnO under the stirring at room
4, and control is 1.5～2.5 hours the joining day, stirring at room reaction 10～15h, 40～50 ℃ of following stirring reactions 10～15 hours, filtered while hot, hot wash, regulating pH value of filtrate is 1～2, and this moment, the adularescent solid was separated out, and filtered, cold water washing, 95 ℃ slowly drip 2mol/L hydrochloric acid down and dissolve filtered while hot to white solid, leaving standstill the adularescent solid under 0～5 ℃ separates out, be difunctional organic ligand 2,4,6-pyridine tricarboxylic acid PTA.
A kind of water-soluble rare-earth fluorescence labeling material adopts difunctional organic ligand 2,4 according to claim 1, and the 6-pyridine tricarboxylic acid is a part, it is characterized in that the structural formula of this rare-earth fluorescence labeling material is:
A. the sour sodium binary complex of europium (III), i.e. Na are closed in three (2,4, the 6-pyridine tricarboxylic acid)
6[Eu (PTA)
3], concrete structure is:
B. the sour sodium binary complex of terbium (III), i.e. Na are closed in three (2,4, the 6-pyridine tricarboxylic acid)
6[Tb (PTA)
3], concrete structure is:
A kind of method for preparing above-mentioned rare-earth fluorescence labeling material is characterized in that the concrete steps of this method are: with 2,4,6-pyridine tricarboxylic acid PTA is dissolved in the 2mol/L hydrochloric acid soln, treats that solid all after the dissolving, slowly drips EuCl
3The aqueous solution or TbCl
3The aqueous solution; EuCl wherein
3Or TbCl
3With the mol ratio of PTA be 1:3; Regulator solution pH to 8～9,40～60 ℃ stirring in water bath 8 hours is filtered, leave standstill under the room temperature treat that it separates out after, washing, vacuum-drying, white solid Na
6[Eu (PTA)
3] or Na
6[Eu (PTA)
3].
The rare-earth fluorescence labeling material PTA:Eu that the present invention is prepared
3+And PTA:Tb
3+Has very strong fluorescence intensity and bigger fluorescence quantum yield, good water-solubility, stability, thereby be easy to do biomolecular labeling, little to the influence of the biomolecules of institute's mark, can be applicable to the detection of labelled immune analysis, nucleic acid determination, medical diagnosis on disease, bacterium, virus, microorganism etc.；
Preparation method's technology of the present invention is simple, and cost is low and facility investment is few, not with an organic solvent, can not pollute environment; Therefore has practical significance aspect its range of application of expansion.
Description of drawings
Fig. 1 is Na
6[Eu (PTA)
3] excitation spectrum and emmission spectrum (5300PC, muting sensitivity excite and launch slit to be 1.5nm) under solid state.Wherein (a) is excitation spectrum; (b) be emmission spectrum.
Fig. 2 is Na
6[Tb (PTA)
3] excitation spectrum and emmission spectrum (5300PC, muting sensitivity excite and launch slit to be 1.5nm) under solid state.Wherein (a) is excitation spectrum; (b) be emmission spectrum.
Embodiment
Below the invention will be further described with example, but be not limited thereto.
Embodiment one: difunctional organic ligand 2,4, and 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, with 2 and deionized water by volume 1:20 mix, stirring at room takes by weighing an amount of KMnO
4Slowly add in the above-mentioned mixing solutions (the control joining day is 2h), stirring at room 10～15h afterwards, 40～50 ℃ are stirred 10～15h, filtered while hot down, hot wash three times, filtrate transfers to pH=1～2 with HCl solution, and white solid is separated out, and filters, cold water washing three times, 95 ℃ drip down slowly HCl and dissolve until most of white solid, and filtered while hot leaves standstill adularescent solid (PTA) under 0～5 ℃ and separates out.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 (45.51), N:5.64 (6.63), H:3.65 (2.39), 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): δ H 8.52 (s, 2H, py).
Embodiment two: Na
6[Eu (PTA)
3] 18H
2The concrete preparation method of O is as follows:
1.2mmol PTA is dissolved in a small amount of rare HCl solution, treats that solid all after the dissolving, adds deionized water and makes the system cumulative volume reach 50mL.Then with 2.0mL (0.4mmol) EuCl
3The aqueous solution slowly is added drop-wise in the above-mentioned PTA solution, uses 1.0molL
-1The NaOH aqueous solution transfers to pH about 8～9, and 60 ℃ of stirring in water bath 8 hours leave standstill a couple of days under the room temperature, separate out clear crystal Na
6[Eu (PTA)
3] 18H
2O, productive rate 60%.
Ultimate analysis: EuNa
6C
24H
6N
3O
18(Na
6[Eu (PTA)
3]), experimental value (theoretical value) C:23.2 (34.10), N:3.41 (4.97), H:3.28 (0.72), C/N6.80 (6.86) .IR (KBr)/cm
-1: 3427.1 (v
COO-H), 1618.3 (v
C=O), 1365.8 (v
C=O), 1556.4 (v
C=N, in Py), 1439.9 (v
C=C, in Py), 467.4 (v
Eu-O).
Embodiment three: Na
6[Tb (PTA)
3] 18H
2The concrete preparation method of O is as follows:
Na among this preparation method and the embodiment two
6[Eu (PTA)
3] 18H
2The preparation method of O is basic identical, and different is: with the EuCl among the embodiment two
3The aqueous solution changes TbCl into
3The aqueous solution.
Ultimate analysis: TbNa
6C
24H
6N
3O
18(Na
6[Tb (PTA)
3]), experimental value (theoretical value) C:23.1 (33.82), N:3.38 (4.93), H:3.28 (0.71), C/N6.84 (6.86) .IR (KBr)/cm
-1: 3441.5 (v
COO-H), 1625.6 (v
C=O), 1366.8 (v
C=O), 1557.2 (v
C=N, in Py), 1436.6 (v
C=C, in Py), 455.7 (v
Eu-O), 405.3 (v
Eu-N).
Referring to Fig. 1 and Fig. 2, from figure, can draw: synthetic rare-earth fluorescence labeling material dual-functional group Na of the present invention
6[Eu (PTA)
3] 18H
2O sends intensive Eu under the exciting of UV-light
3+The red fluorescence of feature, the strongest emission peak is positioned at 618nm; Rare-earth fluorescence labeling material dual-functional group Na
6[Tb (PTA)
3] 18H
2O sends intensive Tb under the exciting of UV-light
3+The green fluorescence of feature, the strongest emission peak is positioned at 543nm.
Claims (4)
1. difunctional organic ligand 2,4, the 6-pyridine tricarboxylic acid is characterized in that the structural formula of this organic ligand is:
2. one kind prepares difunctional organic ligand 2,4 according to claim 1, and the method for 6-pyridine tricarboxylic acid is characterized in that the concrete steps of this method are: 2 is dissolved in the deionized water, slowly adds oxygenant KMnO under the stirring at room
4, and control is 1.5～2.5 hours the joining day, stirring at room reaction 10～15h, 40～50 ℃ of following stirring reactions 10～15 hours, filtered while hot, hot wash, regulating pH value of filtrate is 1～2, and this moment, the adularescent solid was separated out, and filtered, cold water washing, 95 ℃ slowly drip the 2mol/L hydrochloric acid soln down and dissolve filtered while hot to white solid, leaving standstill the adularescent solid under 0～5 ℃ separates out, be difunctional organic ligand 2,4,6-pyridine tricarboxylic acid PTA.
3. a water-soluble rare-earth fluorescence labeling material adopts difunctional organic ligand 2,4 according to claim 1, and the 6-pyridine tricarboxylic acid is a part, it is characterized in that the structural formula of this rare-earth fluorescence labeling material is:
A. the sour sodium binary complex of europium (III), i.e. Na are closed in three (2,4, the 6-pyridine tricarboxylic acid)
6[Eu (PTA)
3], concrete structure is:
B. the sour sodium binary complex of terbium (III), i.e. Na are closed in three (2,4, the 6-pyridine tricarboxylic acid)
6[Tb (PTA)
3], concrete structure is:
4. method for preparing rare-earth fluorescence labeling material according to claim 3, it is characterized in that the concrete steps of this method are: with 2,4,6-pyridine tricarboxylic acid PTA is dissolved in the 2mol/L hydrochloric acid soln, treats that solid all after the dissolving, slowly drips EuCl
3The aqueous solution or TbCl
3The aqueous solution; EuCl wherein
3Or TbCl
3With the mol ratio of PTA be 1:3; Regulator solution pH to 8～9,40～60 ℃ stirring in water bath 8 hours is filtered, leave standstill under the room temperature treat that it separates out after, washing, vacuum-drying, white solid Na
6[Eu (PTA)
3] or Na
6[Eu (PTA)
3].
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|---|---|---|---|
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Cited By (5)
| 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 |
| CN102731479A (en) * | 2012-06-04 | 2012-10-17 | 上海大学 | Organic ligand, rare earth organic fluorescent probe material thereof and preparation method thereof |
| CN103265580A (en) * | 2013-05-24 | 2013-08-28 | 南开大学 | Method for preparing porous europium-manganese coordination polymer material and application thereof |
| KR101735405B1 (en) * | 2014-08-22 | 2017-05-15 | 나노씨엠에스(주) | Luminescence rare earth compound and dichroic phosphor composition comprising the same |
| CN112521937A (en) * | 2020-12-10 | 2021-03-19 | 四川师范大学 | Preparation and application of rare earth fluorescent composite material for uric acid detection |
-
2009
- 2009-01-04 CN CNA2009100448125A patent/CN101445480A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| CUI-JIN LI,A MENG-XIA PENG,AB JI-DONG LENG ET AL: "Synthesis, structure, photoluminescence and magnetic properties", 《CRYSTENGCOMM》 * |
| 安保礼、罗一帆、叶剑清等: "稀土配合物Na3Eu(DPA)3掺杂的PMMA树脂的制备及其发光性能", 《中国稀土学报》 * |
Cited By (8)
| 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 |
| CN102731479A (en) * | 2012-06-04 | 2012-10-17 | 上海大学 | Organic ligand, rare earth organic fluorescent probe material thereof and preparation method thereof |
| CN102731479B (en) * | 2012-06-04 | 2013-11-20 | 上海大学 | Organic ligand, rare earth organic fluorescent probe material thereof and preparation method thereof |
| CN103265580A (en) * | 2013-05-24 | 2013-08-28 | 南开大学 | Method for preparing porous europium-manganese coordination polymer material and application thereof |
| CN103265580B (en) * | 2013-05-24 | 2016-01-20 | 南开大学 | The preparation method of porous europium-manganese coordination polymer material and application thereof |
| KR101735405B1 (en) * | 2014-08-22 | 2017-05-15 | 나노씨엠에스(주) | Luminescence rare earth compound and dichroic phosphor composition comprising the same |
| CN112521937A (en) * | 2020-12-10 | 2021-03-19 | 四川师范大学 | Preparation and application of rare earth fluorescent composite material for uric acid detection |
| CN112521937B (en) * | 2020-12-10 | 2022-07-19 | 四川师范大学 | Preparation and application of rare earth fluorescent composite material for uric acid detection |
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Application publication date: 20090603 |