CN101101291A - Three-D nano hole Eu coordinate polymer type zinc ion fluorescent probe and its preparation method and uses - Google Patents
Three-D nano hole Eu coordinate polymer type zinc ion fluorescent probe and its preparation method and uses Download PDFInfo
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- CN101101291A CN101101291A CNA2007100581508A CN200710058150A CN101101291A CN 101101291 A CN101101291 A CN 101101291A CN A2007100581508 A CNA2007100581508 A CN A2007100581508A CN 200710058150 A CN200710058150 A CN 200710058150A CN 101101291 A CN101101291 A CN 101101291A
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- type zinc
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Abstract
The invention relates to a fluorescent probe of three-dimensional nanometer void, ion of Eu coordination polymer type and the method of preparation and application. The fluorescent probe of ion of Eu coordination polymer type is chemical formula which is {Eu(TDA)1.5(H2O)2}n(TDA is equal to 2, 5 hyphen thiofuran dicarboxylic acid),it has the structure of three-dimensional nanometer void. When add ZnCl2 in the N, N-dimethylformamide liquor of complexes, the place of luminescence emission peak is not changed, the intensity of the locate 596nm of emission peak enhance evidently with the deepness of Zn2+ ion. The fluorescent probe has great application value in the area of life sciences and industry.
Description
[technical field]
The present invention relates to three-D nano hole Eu coordinate polymer type zinc ion fluorescence probe and preparation method thereof and application, it is a rare earth based microporous coordination polymer type zinc ion fluorescent, is with a wide range of applications at life science.
[background technology]
Because distinctive 4f electronic structure of rare earth ion and 4f electronics are subjected to the bigger shielding effect of outer-shell electron and are subjected to part field slight influence, also have the stronger factors such as magnetic anisotropy of rare earth ion to make rare earth compound that very narrow fluorescence emission peak generally all be arranged, rare earth compound has been widely used in [G.Vicentini etc. among all kinds of photoelectric devices and the equipment as luminescent material, Coord.Chem.Rev., 196,353,2000].As can be used as biological fluorescent labeling, being used to detect for rare earth ion is the ion concentration [P.B.Glover etc., J.Am.Chem.Soc.125,9918,2003] of photosensitive ion, also is widely used in medical science.Therefore the fluorescence probe that designs synthesizing efficient has in recent years become the common objective that the various countries scientist pursues.
[summary of the invention]
The purpose of this invention is to provide an a kind of three-D nano hole Eu coordinate polymer type zinc ion fluorescence probe and preparation method and purposes.It is a rare earth based microporous coordination polymer type zinc ion fluorescent.The present invention selects 2 for use, the synthetic Eu coordination polymer with three-D nano hole structure of 5-thiophene dicarboxylic acid part.As N, add ZnCl in N '-dimethyl formamide solution at complex
2The time, the invariant position of fluorescence emission peak, the 598nm emission peak (
5D
0→
7F
1) intensity along with Zn
2+The increase of ion concentration and significantly strengthening.This Eu complex can be used as Zn
2+The fluorescence probe of ion is with a wide range of applications at life science.
The present invention be address the above problem the scheme that is adopted be the design a kind of three-D nano hole Eu coordinate polymer type zinc ion fluorescence probe.It is characterized in that it is the compound of following chemical formula: { Eu (TDA)
1.5(H
2O)
2}
n, TDA=2 wherein, 5-thiophene dicarboxylic acid part; The decomposition temperature of this fluorescence probe is 400 ℃, and main infrared absorption peak is: 3600-3300cm
-1, 3105cm
-1, 1642cm
-1, 1539cm
-1, 1394cm
-1, 1328cm
-1
Described compound structure is: crystal belongs to monoclinic system, and space group is C 2/c, and cell parameter is: a=25.3124 (36) , b=5.8154 (9) , c=18.9479 (27) , B=124.08 (0) °; { Eu (TDA)
1.5(H
2O)
2}
nThree-dimensional structure in, each Eu ion with from six carboxyl oxygen atoms and two hydrone coordinations of TDA part, form the eight-coordinate environment.There are two kinds of coordination modes in TDA, a kind of be two carboxyls respectively huge legendary turtle close two Eu ions, another kind be two carboxyls all with the monodentate coordination, connect four Eu ions.The coordination mode that TDA is abundant is dressed up the tridimensional network of high-sequential to the Eu ion set, and presents the nanoscale tubular structure of rule.In [100] direction, they present a, b and three kinds of holes that vary in size of c, as shown in Figure 2.And, then present another kind of novel dumbbell shaped pore passage structure in [010] direction.
The invention also discloses the preparation method of three-D nano hole Eu coordinate polymer type zinc ion fluorescence probe, it is characterized in that it comprises the steps:
1) with Eu (NO
3)
36H
2O, TDA transferred in the polytetrafluoroethylliner liner of hydrothermal reaction kettle in 1: 1.5～2.5 the ratio and the potpourri of deionized water, 155-165 ℃ of reaction 68-72 hour;
2) programmed cooling 0.5-1.0 ℃/hour up to room temperature, and filtration washes with water, target product.
Three-D nano hole Eu coordinate polymer type zinc ion fluorescence probe of the present invention is introduced Zn
2+, make Eu
3+Ion significantly strengthens in the fluorescent emission at 596nm place, so to Zn
2+That the fluorescence probe effect is arranged is Eu
3+The 596nm launch window, rather than 618nm launch window.
Three-D nano hole Eu coordinate polymer type zinc ion fluorescence probe of the present invention can be applied in the probe biomolecule.
The invention has the beneficial effects as follows:
(1) fluorescence probe of the present invention obtains under hydrothermal condition, has very high thermal stability.Thermogravimetric analysis only shows at 400 ℃, { Eu (TDA)
1.5(H
2O)
2}
nJust can decompose.The more existing fluorescent material of this point is more superior.
(2) based on the high sensitivity and the high selectivity of rare earth ion fluorescence spectrum, its development and application and life science are closely related.Eu in the rare earth element and Tb instead radioactive isotope and nonisotopically labelled fluorescence probe have very big potentiality.Particularly the Tb ion has been widely used in the effect and the function thereof of Mg ion in researching DNA and the biosome.Use the Eu rare earth ion to have the quantum yield height as the fluorescence probe of biomolecule, the Stokes displacement is big, and emission peak is narrow, excites and advantages such as emission wavelength ideal and fluorescence lifetime length.
(3) reported Cl in recent years
-, H
+, K
+, Ag
+, Zn
2+, Mg
2+, Cu
2+, Hg
2+Plasma has optionally fluorescence probe, when the concentration of these ions increases, can cause the change of corresponding rare earth ion fluorescence intensity, thereby determines such contained ion concentration in the system.A three-dimensional coordination polymer of the present invention is for Zn
2+Have the selectivity of height, the intensity of rare earth emission peak is along with Zn
2+Zn is worked as in the increase of ion concentration and significantly strengthening
2+Amount when constantly increasing, emission peak
5D
0→
7F
1Intensity constantly increase.Because Zn
2+Ion extensively is present in the various biology enzymes, and the present invention will open unprecedented space for the application of nanotube-shaped rare earth multidimensional polymeric material.
Peak position that it should be noted that the easy sensitization of Eu ion among the present invention in addition be not electric dipole transition (
5D
0→
7F
2), but magnetic dipole transition (
5D
0→
7F
1).
[description of drawings]
Fig. 1 { Eu (TDA)
1.5(H
2O)
2}
nMolecular structure.
Fig. 2 is in [100] direction, { Eu (TDA)
1.5(H
2O)
2}
nThree-dimensional open-framework figure.
Fig. 3 is in [010] direction, { Eu (TDA)
1.5(H
2O)
2}
nThree-dimensional manometer tubular structure figure.
Fig. 4 complex is at different Zn
2+Fluorescence spectrum under the concentration.
[embodiment]
Fluorescent probe molecule formula disclosed by the invention is: { Eu (TDA)
1.5(H
2O)
2}
n, TDA=2 wherein, 5-thiophene dicarboxylic acid part.The decomposition temperature of this fluorescence probe is 400 ℃, and main infrared absorption peak is: 3600-3300cm
-1, 3105cm
-1, 1642cm
-1, 1539cm
-1, 1394cm
-1, 1328cm
-1
Fluorescence probe structure disclosed by the invention as shown in Figure 1, crystal belongs to monoclinic system, space group is C2/c, cell parameter is: a=25.3124 (36) , b=5.8154 (9) , c=18.9479 (27) , β=124.08 (0) °; At { Eu (TDA)
1.5(H
2O)
2}
nIn the three-dimensional structure, five TDA negative ion of each Eu ion chelating and two hydrones form eight-coordinate, each TDA negative ion one end connects two Eu ions by carboxyl oxygen, the other end is by Eu of carboxyl oxygen chelating, be assembled into the tridimensional network of high-sequential, and three kinds of different big or small holes that present rule, wherein the maximum length of duct a reaches 1.4nm, as shown in Figure 2.
Preparation method of the present invention comprises the steps:
1) with Eu (NO
3)
36H
2O, TDA transfer in the polytetrafluoroethylliner liner of hydrothermal reaction kettle in 1: 1.5～2.5 the ratio and the potpourri of deionized water;
2) under 155-165 ℃, after constant temperature 68-72 hour, carry out programmed cooling up to room temperature, 0.5-1.0 ℃/hour;
3) products therefrom filters and washes with water, obtains laminar crystal, is target product.
Synthesizing of embodiment 1 complex:
With 0.3mmol TDA, 0.2mmol Eu (NO
3)
36H
2The potpourri of O and 10mL water is transferred in the polytetrafluoroethylliner liner of 20mL hydrothermal reaction kettle, and under 160 ℃, constant temperature carried out programmed cooling up to room temperature, 0.5 ℃/h after 72 hours.Products therefrom filters and washes with water, obtains light brown laminar crystal.
The sign of embodiment 2 complexs:
(1) structure determination of complex
BRUKER SMART 1000 x-ray diffractometers are adopted in crystal structure determination, use Mok alpha ray (λ=0.71073 ) to be incident radiation through the graphite monochromatization, collect point diffraction with ω-2 θ scan mode, obtain cell parameter through least-squares refinement, utilize the SHELXL-97 direct method to solve crystal structure from the difference Fourier electron-density map, and through Lorentz and polarization effect correction.All H atoms are synthetic and definite through desirable position calculation by difference Fourier.Detailed axonometry data see Table 1.Structure is seen Fig. 1, Fig. 2 and Fig. 3; Fig. 1: { Eu (TDA)
1.5(H
2O)
2}
nMolecular structure.Fig. 2 and Fig. 3: { Eu (TDA)
1.5(H
2O)
2}
n3 D pore canal and nano tubular structure figure.
The crystallographic data of table 1 complex
| ?Empirical?formula ?Identification?code ?Formula?weight ?Temperature ?Wavelength ?Crystal?System ?Space?group ?Unit?cell?Dimensions ?Volume ?Z ?Density(calculated) ?Absorption?coefficient | C 9H 6EuO 8S 1.50 060804C 442.19 274(2)K 0.71073 monoclinic C2/c a＝25.312(4) b＝5.8154(9) c＝18.948(3) β＝124.08(0)° 2310.17(60) 3 8 2.543Mg/m 3 5.736mm -1 |
| ?F(000) ?Crystal?size(mm 3) ?θ ?Limiting?indices ?Reflections?collected/unique ?Refinement?method ?Data/restraints/parameters ?Goodness-of-fit?on?F 2?Final?R?indices[I＞2σ(I)] ?Rindices(all?data) ?Largest?diff.Peak?and?hole | 1668 0.15×0.20×0.12mm 2.20?to?26.39° -24＜＝h＜＝31，-5＜＝k＜＝7， -23＜＝l＜＝22 6186/2353[R(int)＝0.0960] Full-matrix?least-squares?on?F 2 2353/4/194 1.070 R1＝0.0423. wR2＝0.0972 R1＝0.0479. wR2＝0.1007 2.976and-2.848e. -3 |
(2) photoluminescent property of complex
With Cary Eclipse type fluorescent spectrophotometer assay the photoluminescent property of complex, surveyed the solution spectrum of complex in the DMF solvent, excitation wavelength all during as excitaton source, has obtained Eu with 296nm
3+Emission spectrum, pure complex solution fluorescence Spectra is shown in Fig. 4, emission peak can be assigned as respectively 596,616 and the 700nm place
5D
0→
7F
1,
5D
0→
7F
2,
5D
0→
7F
4When in the DMF of complex solution, adding ZnCl
2The time, 596nm place emission peak peak position with do not add Zn
2+In time, compared, and any moving do not taken place, but the 596nm place
5D
0→
7F
1The luminous intensity at peak is along with Zn
2+Concentration increase and significantly strengthen, and other peak is constantly weakening, as shown in Figure 4.This shows that this compound is to Zn
2+Very strong fluorescence selectivity is arranged, thereby expectation can be as Zn
2+Fluorescence probe.
Claims (6)
1, a kind of three-D nano hole Eu coordinate polymer type zinc ion fluorescence probe is characterized in that it is the compound of following chemical formula: { Eu (TDA)
1.5(H
2O)
2}
n, TDA=2 wherein, 5-thiophene dicarboxylic acid part; The decomposition temperature of this fluorescence probe is 400 ℃, and main infrared absorption peak is: 3600-3300cm
-1, 3105cm
-1, 1642cm
-1, 1539cm
-1, 1394cm
-1, 1328cm
-1
2, three-D nano hole Eu coordinate polymer type zinc ion fluorescence probe according to claim 1 is characterized in that described compound structure is:
Crystal belongs to monoclinic system, and space group is C2/c, and cell parameter is: a=25.3124 (36) , b=5.8154 (9) , c=18.9479 (27) , β=124.08 (0) °; { Eu (TDA)
1.5(H
2O)
2}
nThree-dimensional structure in, each Eu ion with from six carboxyl oxygen atoms and two hydrone coordinations of TDA part, form the eight-coordinate environment, the Eu ion set is dressed up the tridimensional network of high-sequential, and presents the nanoscale tubular structure of rule.
3, three-D nano hole Eu coordinate polymer type zinc ion fluorescence probe according to claim 1, two kinds of coordination modes that it is characterized in that described TDA, two carboxyls of a kind of TDA of being huge legendary turtle respectively close two Eu ions, another kind be two carboxyls all with the monodentate coordination, connect four Eu ions.
4, the preparation method of the described three-D nano hole Eu coordinate polymer type zinc ion fluorescence probe of claim 1 is characterized in that it comprises the steps:
1) with Eu (NO
3)
36H
2O, TDA transferred in the polytetrafluoroethylliner liner of hydrothermal reaction kettle in 1: 1.5～2.5 the ratio and the potpourri of water, 155-165 ℃ of reaction 68-72 hour;
2) programmed cooling 0.5-1.0 ℃/hour up to room temperature, and filtration washes with water, target product.
5, the application of the described three-D nano hole Eu coordinate polymer type zinc ion fluorescence probe of claim 1 in probe biomolecule.
6, the application of three-D nano hole Eu coordinate polymer type zinc ion fluorescence probe according to claim 5 in probe biomolecule is characterized in that introducing Zn
2+, Eu
3+Ion significantly strengthens in the fluorescent emission at 596nm place.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079752A (en) * | 2010-12-17 | 2011-06-01 | 沈阳化工大学 | Synthesis method of rare-earth coordination polymer with functions of mercury ion fluorescence probe |
| CN102507525A (en) * | 2011-11-28 | 2012-06-20 | 齐齐哈尔大学 | Novel method for constructing Zn2+ ratio detecting system by solubilizing fluorescent probe in micelle |
| CN106543211A (en) * | 2016-10-26 | 2017-03-29 | 桂林理工大学 | Chemical formula is [EuC9O8H10N]nMetal organic framework compound and its preparation method and application |
| CN107057083A (en) * | 2017-05-18 | 2017-08-18 | 洛阳师范学院 | A kind of micropore terbium coordination polymer fluorescence identifying material and preparation method |
| CN107603602A (en) * | 2017-10-31 | 2018-01-19 | 江西省科学院应用化学研究所 | A kind of zinc rare earth metal organic frame fluorescent sensing material and its synthetic method |
| CN107674213A (en) * | 2017-10-01 | 2018-02-09 | 桂林理工大学 | A kind of La MOF materials and preparation method with double parts |
| CN110951084A (en) * | 2018-09-27 | 2020-04-03 | 天津工业大学 | Application of white-light-emitting double-rare-earth metal organic framework material in detection of phenol pollutants |
| CN110951083A (en) * | 2018-09-26 | 2020-04-03 | 天津工业大学 | Double-rare-earth metal organic framework material based on white light emission and preparation method thereof |
| CN113527698A (en) * | 2021-06-03 | 2021-10-22 | 西安石油大学 | Europium (III) metal organic framework Eu-MOF probe material and preparation method and application thereof |
-
2007
- 2007-07-16 CN CNA2007100581508A patent/CN101101291A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079752A (en) * | 2010-12-17 | 2011-06-01 | 沈阳化工大学 | Synthesis method of rare-earth coordination polymer with functions of mercury ion fluorescence probe |
| CN102079752B (en) * | 2010-12-17 | 2013-02-20 | 沈阳化工大学 | Synthesis method of rare-earth coordination polymer with functions of mercury ion fluorescence probe |
| CN102507525A (en) * | 2011-11-28 | 2012-06-20 | 齐齐哈尔大学 | Novel method for constructing Zn2+ ratio detecting system by solubilizing fluorescent probe in micelle |
| CN106543211A (en) * | 2016-10-26 | 2017-03-29 | 桂林理工大学 | Chemical formula is [EuC9O8H10N]nMetal organic framework compound and its preparation method and application |
| CN107057083A (en) * | 2017-05-18 | 2017-08-18 | 洛阳师范学院 | A kind of micropore terbium coordination polymer fluorescence identifying material and preparation method |
| CN107674213A (en) * | 2017-10-01 | 2018-02-09 | 桂林理工大学 | A kind of La MOF materials and preparation method with double parts |
| CN107603602A (en) * | 2017-10-31 | 2018-01-19 | 江西省科学院应用化学研究所 | A kind of zinc rare earth metal organic frame fluorescent sensing material and its synthetic method |
| CN107603602B (en) * | 2017-10-31 | 2019-08-27 | 江西省科学院应用化学研究所 | A kind of zincium-rare earth metal-organic framework fluorescent sensing material and its synthetic method |
| CN110951083A (en) * | 2018-09-26 | 2020-04-03 | 天津工业大学 | Double-rare-earth metal organic framework material based on white light emission and preparation method thereof |
| CN110951084A (en) * | 2018-09-27 | 2020-04-03 | 天津工业大学 | Application of white-light-emitting double-rare-earth metal organic framework material in detection of phenol pollutants |
| CN113527698A (en) * | 2021-06-03 | 2021-10-22 | 西安石油大学 | Europium (III) metal organic framework Eu-MOF probe material and preparation method and application thereof |
| CN113527698B (en) * | 2021-06-03 | 2022-07-19 | 西安石油大学 | Europium (III) metal organic framework Eu-MOF probe material and preparation method and application thereof |
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