CN1707244B - A titanium oxide nano-europium (Eu) fluorescent probe - Google Patents
A titanium oxide nano-europium (Eu) fluorescent probe Download PDFInfo
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- CN1707244B CN1707244B CN 200410020716 CN200410020716A CN1707244B CN 1707244 B CN1707244 B CN 1707244B CN 200410020716 CN200410020716 CN 200410020716 CN 200410020716 A CN200410020716 A CN 200410020716A CN 1707244 B CN1707244 B CN 1707244B
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Abstract
The present invention relates to inorganic-organic hybridized fluorescent nanometer titania particle, and is especially fluorescent nanometer titania-europium probe and its application. Silane reagentis first reacted with trivalent europium-beta-diketone fluorescent complex to form fluorescent precursor, and then, through sol-gel reaction with titanate in alcohol-water solution, one kind of strongfluorescent nanometer particle with active radical as biological marker in the surface is produced. Thus produced fluorescent nanometer titania particle has fluorescent life of about 400 ms and fluor escent quantum yield up to 11 %. The fluorescent nanometer titania particle may be used as biological molecular fluorescent probe for time resolution fluorescent measurement and can eliminate the fluorescent background interference from biological sample. The present invention has important application foreground in various biochemical detection fields.
Description
Technical field
The present invention relates to can be used for the nanometer europium fluorescence probe of biomolecular labeling, specifically a kind of nano titania europium fluorescence probe and (biomolecular labeling detection) thereof are used.
Background technology
Sol-gel technique provides valid approach for preparing the inorganic-organic hybridization material at ambient temperature.In recent years, the inorganic-organic hybridization material is in many research fields, especially more and more come into one's own (document 1:U.Narang, R.Wang, P.Prasad, F.Bright, J.Phys.Chem.1994,98,17 of material science and field of nanometer technology; Document 2:H.Yanagi, T.Hishiki, T.Tobitani, A.Otomo, S.Mashiko, Chem.Phys.Lett.1998,292,332.; Document 3:H.R.Li, J.Lin, H.J.Zhang, L.S.Fu, Q.G.Meng, S.B.Wang, Chem.Mater.2002,14,3651; Document 4:K.Kanie, T.Sugimoto, J.Am.Chem.Soc.2003,125,10518).Existing report shows the europium fluorescence complex is wrapping in the inorganic material with sol-gel process, the physics of prepared material, chemistry and mechanical property are greatly improved and improve (document 5:H.Li, S.Inoue, K.Machida, G.Adachi, J.Lumin.2000,87-89,1069; Document 6:L.R.Matthews, E.T.Knobbe, Chem.Mater.1993,5,1697; Document 7:O.A.Serra, E.J.Nassar, G.Zapparolli, I.L.V.Rosa, J.Alloys Compd.1994,207-208,454; Document 8:O.A.Serra, E.J.Nassar, I.L.V.Rosa, J.Luminescence.1997,72-74,263; Document 9:H.H.Li, S.Inoue, K.Machida, G.Adachi, Chem.Mater.1999,11,3171; Document 10:M.M.Silva, V.de Zea Bermudez, L.D.Carlos, A.P.P.deAlmeida, M.J.Smith, J.Mater.Chem.1999,9,1735).Yet, these work only are that the europium fluorescence complex is doped in the inorganic material by physical action, problems such as the complex amount that therefore in use can produce leakage, the fluorescence intensity decline of fluorescence complex and wrap up is less have greatly hindered the application of fluorescent hybridization material aspect biochemistry detection.
Develop rapidly along with modern science and technology, ultramicron, high-sensitivity biological detection technique are to medical science and the important effect of life science play more and more, wherein the namo fluorescence probe technology is one and has important application prospect, supersensitive bioanalysis detection technique, and the namo fluorescence probe that has developed at present mainly contains (1) semiconductor nano (claiming quantum dot again); (2) be surrounded by the composite Nano fluorescence probe (wherein a class is the high molecule plastic namo fluorescence probe, and another kind of is the nanometer silica gel particulate of interior bag three bipyridine ruthenium fluorescence complexs) of fluorescence molecule.These fluorescence probes exist sensitivity lower, luminous easy flicker, the labeling process complexity, fluorescence molecule leaks and serious problems such as background fluorescence interference easily, and the europium fluorescence complex (document 11: Yuan Jingli that Yuan Jingli etc. develop recently, Wang Guilan, trivalent europium-beta-diketone fluorescent label thing and application thereof, Chinese invention patent, application number: 02132910.9), the exciting light energy that absorbs can be passed to the center europium ion expeditiously, it had both had than the hyperfluorescence performance, has the reactive group that can be used for mark again, and what successfully it has been prepared into the covalent bond mould assembly is the inorganic-organic hybridization fluorescent material (document 12: Yuan Jingli of host material with silicon dioxide, Tan Mingqian, Hai Xiaodan, Wang Guilan, beta-diketon-trivalent europium complex namo fluorescence probe and preparation and application, Chinese invention patent, application number: 03133857.7).Its great advantage can be used for time-resolved fluorometry exactly, eliminates the influence to measuring of various light at random and short life fluorescence fully, measures sensitivity thereby greatly improve.
But, existing inorganic-research work of organic fluorescence hybrid material mainly based on the silicon dioxide inorganic material as skeleton structure, seldom relate to other inorganic material.Titanium oxide inorganic materials chemistry character is stable, has the performance of excellent absorption ultraviolet light, has been widely used in aspects such as senior pigment, cosmetics.Utilize the alkoxytitanium acid esters titanium dioxide nano-particle that hydrolysis is prepared in pure water, because electrostatic force, Van der Waals force and the mutual repulsive force of short distance etc. cause nano particle easily to be reunited, monodispersity descends.Recently, people such as Eiden-Assmann have studied influence (the document 13:S.Eiden-Assmann of solution ion strength to preparation nano-titania particle size in great detail, J.Widoniak, G.Maret, Chem.Mater.2004,16,6), but utilize the control solution ion strength to realize with titania is the controlled technology of preparing of the luminescent nanoparticle of matrix, and with TiO
2Nanoparticle is applied to biochemistry detection as the biomolecular labeling material and does not appear in the newspapers.
Summary of the invention
At above problem, the object of the present invention is to provide a kind of is hybridized nanometer europium fluorescence probe and the controlled preparation and the biomolecular labeling detection application of host material with titania
To achieve these goals, the technical solution used in the present invention is:
A kind of nano titania europium fluorescence probe, it is to prepare by following operating process, at first form the fluorescence presoma, and then itself and titanate esters generation sol gel reaction are prepared into hybridized nanometer europium fluorescent particle by silylating reagent (mostly being the compound that contains the tri-alkoxy silicon group) and the reaction of trivalent europium-beta-diketone class fluorescence complex generation covalent bonding; The monomer and the titanate esters of described trivalent europium ion, beta-diketon organic ligand, silylating reagent, the molar ratio between them are 1: 2～3 (mol ratio of trivalent europium ion and four tooth beta-diketons and bidentate beta-diketon organic ligand was respectively 1: 2 and 1: 3): 5-50: 200-1000.
Described can be 3-aminopropyl tri-alkoxy silicon or [2-(2-aminoethylamino) ethylamino] propyl trimethoxy silicane etc. with the monomer of the silylating reagent of titanate esters copolymerization, and the molecular formula of described titanate esters is Ti (OR)
4, R wherein is-C
nH
2n+1, n=1～5.
Described beta-diketon organic ligand is bidentate beta-diketone compounds or four tooth beta-diketone compounds;
The bidentate beta-diketone compounds, structural formula can be expressed as follows:
R in the formula
1=C
6F
5Or fat hydrocarbon substituting group C
nH
2n+1, C
nF
2n+1, n=1,2,3,4 or 5 wherein;
R
2Be the arene substituting group
One of in;
R
3Be chlorosulfonyl (SO
2Cl), different sulphur itrile group (NCS), amino (NH
2) or hydrazine sulfonyl (SO
2NHNH
2);
Four tooth beta-diketone compounds, structural formula can be expressed as follows:
R in the formula
4Be chlorosulfonyl (SO
2Cl), different sulphur itrile group (NCS), amino (NH
2) or hydrazine sulfonyl (SO
2NHNH
2); R
5=C
6F
5Or fat hydrocarbon substituting group C
nH
2n+1, C
nF
2n+1N=1,2,3,4 or 5 wherein.
Titania is that the concrete preparation process of the hybridized nanometer europium fluorescence probe of host material is:
At ambient temperature, with beta-diketon and the reaction of silylating reagent generation covalent bond, their consumption mol ratio is 1: 5～1: 50, and the volumetric molar concentration of beta-diketon is 50～500 μ mol/L in the system, makes the fluorescence precursor; Then fluorescence precursor, titanate esters are joined and contain EuCl
3Alcohol-water (volume ratio is 250: 1) solution in, stirred down room temperature reaction 4～24 hours, centrifuging gets final product.
The present invention is a luminescent substance with trivalent europium and the formed hyperfluorescence complex of beta-diketon class ligand, adopt the method for chemical covalent bonding the europium fluorescence complex to be securely fixed in the network structure of nano titanium oxide, prepare nano titania europium fluorescence probe by simple sol-gel technique, and simultaneously nano-particle surface import can with the active function groups of biomolecule covalent bonding.
The consumption mol ratio of described beta-diketon and silylating reagent is 1: 5～1: 50; Described alcohol is methyl alcohol, ethanol or isopropyl alcohol.
Nano titania europium fluorescence probe of the present invention is used for the labeling method of biomolecule, with titania hybrid nano fluorescent microparticulate in 0.1mol/L～0.05mol/L phosphate buffer solution, after supersonic oscillations, add biomolecule, under agitation add glutaraldehyde then, room temperature reaction adds NaBH
4Reduction, room temperature reaction, the back is standby for several times with the phosphate buffer solution washing.Biomolecule is small-molecule drug, amino acid, polypeptide, protein, nucleotide or the nucleic acid of various biologically actives.
Beta-diketon-trivalent europium complex namo fluorescence probe can be used in time-resolved fluorometry.Described time-resolved fluorometry is a time-resolved fluorescent immunoassay, time-resolved fluorescence DNA hybridization assays method, and time-resolved fluorescence microscope imaging determination method, time-resolved fluorescence raji cell assay Raji and time are differentiated the fluorescent biochip determination method.
Nano titania europium fluorescence probe of the present invention has following advantage:
(1) good stability.The present invention adopts the covalent bonding method to be fixed on the europium fluorescence complex in the Nano microsphere firmly, therefore the nanometer europium fluorescence probe that obtains has very stable structure, fluorescence molecule easily takes place and leaks in the nanometer fluorescent microspheres that has solved the method preparation of adopting the physics parcel, and the problem that causes the nano-probe fluorescence intensity to weaken.
(2) luminous intensity height.Owing to adopt beta-diketon class ligand with active function groups and silylating reagent to form presoma in the mode of covalent bonding, carry out copolymerization with titanate esters again, therefore can so that to single nano fluorescent particulate in be fixed with a large amount of beta-diketon-europium complexes, greatly improved the luminous intensity of nanometer europium fluorescence probe.
(3) preparation method is simple.For existing microemulsion preparation method, sol-gel method is more easy, in preparation nano fluorescent particulate (monomer of silylating reagent is excessive with respect to the europium fluorescence complex in presoma), import the active function groups that amino grade can be directly used in the mark of biomolecule once on the surface of nanoparticle, save loaded down with trivial details nano-particle surface modification.
(4) the nano titania fluorescent particle has good dispersiveness.The titanium dioxide nano-particle of the present invention's preparation is not reunited good dispersion in buffer solution.Owing to be to utilize control EuCl
3Concentration in alcohol-water solution, realize control to titanium dioxide nano-particle size and form, therefore realized controlling the purpose of nano particle more dexterously by the ionic strength of regulation and control reactant liquor, avoided introducing the influence of the hybrid fluorescent material character of other exogenous ion pair preparation, simultaneously also solve the problem that causes nano particle easily to be reunited owing to electrostatic force, Van der Waals force and short distance interaction force etc., realized single dispersion.
(5) applied range.The biomolecule that nano-luminescent material of the present invention is used for behind the biomarker can be used for various time-resolved fluorescence Measurements for Biotechnique, as time-resolved fluorescent immunoassay, DNA hybridization assays, cell recognition, microscope imaging mensuration, unicellular in-site detecting, biochip mensuration etc.
Description of drawings
Fig. 1 is the transmission electron microscope photo of titania hybrid nano fluorescent particulate.
Fig. 2 is the conventional fluorescence spectrum (a) and the time resolution fluorescence spectral (b) of titania hybrid nanometer europium fluorescent particle.
Fig. 3 is X-ray powder diffraction figure (A) room temperature of the nanoparticle handled under the condition of different temperatures, (B) 360 ℃ of calcinings 4 hours and (C) 500 ℃ of calcinings 4 hours.
Fig. 4 is the TG-DSC figure of titania hybrid nano fluorescent particulate.
Fig. 5 is the BHHCT ligand, and pure TiO2 nanoparticle and bonding have BHHCT-Eu
3+The infrared spectrogram of titanium oxide nanoparticles.
Fig. 6 is the BHHCT ligand, APTS-BHHCT and APTS-BHHCT-Eu
3+Uv-visible absorption spectra figure.
Fig. 7 is the time-resolved fluorometry curve with titania hybrid nanoparticle mark bovine serum albumin(BSA) BSA molecule.
Fig. 8 is the working curve with titania hybrid nano fluorescent particle marker determination bovine serum albumin(BSA) BSA.
Embodiment
The invention will be further described below by embodiment.Present embodiment only is used for that the present invention will be described, also belongs to scope of the present invention based on the method for same principle and similar raw material.
Embodiment 1
The preparation and the sign of titania hybrid nano fluorescent particulate
(1) preparation of the nano titania fluorescent particle of covalent bonding bidentate europium-beta-diketone class complex:
With 12.0mg bidentate-beta-diketon class ligand
Joining 20 μ l[2-(2-aminoethylamino) ethylamino] in the propyl trimethoxy silicane (APTS), ultrasound wave effect reaction 20 minutes down is then under stirring, with beta-diketon class ligand-APTS combination and 200 μ lEuCl
3(EuCl
3Mole dosage be bidentate-beta-diketon class ligand molar weight 1/3rd) aqueous solution joins in the 50ml ethanol, stir after 10 minutes, add 0.85ml tetraisopropoxy titanium (TTIP), behind the room temperature reaction 24 hours, the hybridized nanometer fluorescent particle of preparation comes out with acetone precipitation, centrifugal collecting precipitation, with ethanol and the washing to remove unreacted raw material.
(2) covalent bonding four tooth BHHCT-Eu
3+The preparation of the nano titania fluorescent particle of complex:
7.1mg BHHCT is joined among the 20 μ l APTS, and the ultrasound wave effect was reacted 20 minutes down, then under stirring, with BHHCT-APTS combination and 200 μ lEuCl
3(EuCl
3Mole dosage be the BHHCT molar weight 1/2nd) aqueous solution joins in the 50ml ethanol, stir after 10 minutes, add 0.85ml tetraisopropoxy titanium (TTIP), behind the room temperature reaction 24 hours, the hybridized nanometer fluorescent particle of preparation comes out with acetone precipitation, centrifugal collecting precipitation, with ethanol and the washing to remove unreacted raw material.
(3) covalent bonding four tooth BCDOT-Eu
3+The preparation of the nano titania fluorescent particle of complex:
7.3mg BCDOT is joined among the 20 μ l APTS, and the ultrasound wave effect was reacted 20 minutes down, then under stirring, with BHHCT-APTS combination and 200 μ lEuCl
3(EuCl
3Mole dosage be the BHHCT molar weight 1/2nd) aqueous solution joins in the 50ml ethanol, stir after 10 minutes, add 0.85ml tetraisopropoxy titanium (TTIP), behind the room temperature reaction 24 hours, the hybridized nanometer fluorescent particle of preparation comes out with acetone precipitation, centrifugal collecting precipitation, with ethanol and the washing to remove unreacted raw material.
(4) property representation of titania hybrid nano fluorescent particulate
(a) form of nano fluorescent particulate and size dimension
Fig. 1 is the transmission electron microscope photo of titania hybrid nano fluorescent particulate, from the visible bonding of photo BHHCT-Eu is arranged
3+The titania hybrid nano fluorescent particulate of complex is a near-spherical, and size is about 100nm, and is better dispersed between the particulate.The size of particulate can wait by ionic strength, the reaction dissolvent that changes reactant liquor and control.
(b) fluorescence spectrum characteristic
Fig. 2 is fluorescence spectrum and the time resolution fluorescence spectral of titania hybrid nano fluorescent particulate in the Tris-HCl (containing 0.05%Tween-20) of 0.05mol/L pH value 9.1 buffer solution.There is serious at random smooth Interference Peaks in the glow peak of the fluorescence spectrum of visible hybridized nanometer particle among the figure, and the glow peak of its time resolution fluorescence spectral does not then thoroughly have the existence of Interference Peaks, and its emission spectrum then is sharp-pointed narrow peak.Free complex B HHCT-Eu
3+Fluorescence spectrum on maximum emission wavelength be 612nm, the maximum emission wavelength of its fluorescence spectrum also is 612nm behind the nano fluorescent particulate and make, wavelength does not change.The fluorescence lifetime of the nano fluorescent particulate that this method makes is 0.394 millisecond after measured, and the fluorescence that the nano fluorescent particulate is described has still kept the feature of the long fluorescence lifetime of europium complex.
(c) crystalline state of hybridized nanometer fluorescent particle
The X-ray powder diffraction measurement result is seen Fig. 3.As seen from the figure, the room temperature condition nano titania fluorescent particle of preparation down is amorphous impalpable structure, still is impalpable structure 360 ℃ of calcinings with nanoparticle after 4 hours, and just be transformed into the Detitanium-ore-type structure after 4 hours through 500 ℃ of calcinings, be entrained with the crystalline structure of a small amount of brookite simultaneously.
(d) the heat analysis of hybridized nanometer fluorescent particle
Thermoanalytical experimental result (see figure 4) shows obviously has water to exist in the hybridized nanometer particulate of impalpable structure.The differential scanning calorimetry curve has 3 peaks, and the end since 50 ℃ to 240 ℃ of first peak is an endothermic process, and weightlessness reaches about 20%, and this is because nanoparticle discharges the result of tie water.Second peak about about 330 ℃, is exothermic process greatly, continues weightlessly about 28%, and this is mainly the result that organism such as BHHCT and APTS partly decompose.And the 3rd exothermic peak show and taken place from amorphous crystal transfer to anatase greatly near 490 ℃, and this is consistent with the XRD testing result of nanoparticle after 500 ℃ of calcinings.
(e) infrared spectrum of hybridized nanometer fluorescent particle
Fig. 5 is that BHHCT ligand, pure TiO2 nanoparticle and bonding have BHHCT-Eu
3+The infrared spectrogram of titanium oxide nanoparticles.By Fig. 5 B and C as seen, at 3200and 610cm
-1Two strong absorption peaks be-the flexible and flexural vibrations of OH absorb 1044～1129cm
-1Near be the strong absorption of Ti-O-C and C-O key, the existence of pure oxygen base is described.From the infrared spectrum of two nanoparticles, all can find to be positioned at 1442cm in addition
-1Near-flexural vibrations of C-H and be positioned at 1404cm
-1The flexural vibrations peak of C-O-H near.As seen be positioned at 1231 and 1343cm from the infrared spectrogram (Fig. 5 A) of BHHCT ligand
-1Near C-F characteristic peak, these two peaks also appear at bonding equally BHHCT-Eu
3+On the infrared spectrogram of titanium oxide nanoparticles, among Fig. 5 C at 1609cm
-1Locating more weak peak also is to come from BHHCT-Eu
3+Complex, these all illustrate in the hydridization titanium oxide nanoparticles BHHCT-Eu
3+The existence of complex.
(f) BHHCT ligand, APTS-BHHCT combination and APTS-BHHCT-Eu
3+Uv-visible absorption spectra figure
Compare with the uv-visible absorption spectra figure of BHHCT ligand, a new absorption peak appears in the APTS-BHHCT combination shown in Fig. 6 B at the 261nm place, and the main absorption peak that is positioned at the 337nm place does not change, and this explanation has formed APTS-BHHCT combination (APTS does not absorb at 230-300nm through measuring proof).When adding EuCl
3After, red shift (less absorption peak moves to 274nm from 261nm, maximum absorption band from the 337nm red shift to 340nm) has all taken place in the absorption peak of APTS-BHHCT combination.These all illustrate at APTS-BHHCT-EuCl
3In the solution, formed APTS-BHHCT-Eu
3+The complex-bound body.
Embodiment 2
Use titania hybrid nano fluorescent particulate to measure bovine serum albumin(BSA) (being called for short BSA) as the time-resolved fluorometry of fluorescence probe.
(a) titania hybrid nano fluorescent particulate mark bovine serum albumin(BSA)
3.2mg titania hybrid nano fluorescent microparticulate is arrived in the 0.1mol/L phosphate buffer solution (pH=7.1) of 1.0ml, with supersonic oscillations after 20 minutes, add the 8.5mg bovine serum albumin(BSA), 1% glutaraldehyde (phosphate buffer solution) that under agitation adds 500 μ l then, room temperature reaction 24 hours adds 1.0mgNaBH
4Reduction, room temperature reaction 2 hours, the back is standby for several times with the phosphate buffer solution washing.
(b) detection sensitivity of titania hybrid nano fluorescent particulate mark bovine serum albumin(BSA)
With the titanium oxide nanoparticles-BSA combination BSA concentration of 45 μ l doubling dilutions (from 10
-13To 10
-7Mol/L) join in the hole of 96 microwell plates, in parallel 4 holes that are added to of the solution of each concentration, get the mean value of its fluorescence intensity.At the 0.05mol/L that contains 0.05%Tween 20, the Tris-HCl buffer solution and the 0.05mol/L of pH value 9.1, the dilution curve of the Tris-HCl buffer solution of pH value 9.1 is seen Fig. 7.Measuring with instrument is Perkin Elmer VICTOR 1420 multiple labeling calculating instruments (PerkinElmer LifeScience company products), and condition determination is: excitation wavelength, 340nm; Detect wavelength, 615nm; Delay time, 0.2ms; The window time, 0.4ms; Cycling time, 1.0ms.3 times of the standard deviation (SD) of the fluorescence signal during with zero-dose (background) are calculated the minimum lower limit that detects that BSA measures, and the minimum lower limit that detects that gets this law is respectively 6.2 * 10
-12Mol/L (at the 0.05mol/L of 0.05%Tween 20, in the Tris-HCl buffer solution of pH value 9.1) and 9.1 * 10
-12Mol/L (at 0.05mol/L, in the Tris-HCl buffer solution of pH value 9.1).
(c) bovine serum albumin(BSA) solid phase time-resolved fluorometry
In order to investigate the nano titania fluorescent particle is used for solid phase time-resolved fluorescence biochemistry detection as fluorescence probe possibility, with 0.05mol/L, titanium oxide nanoparticles-BSA the combination of the Tris-HCl buffer solution dilution of pH value 9.1 joins in the microwell plate, room temperature reaction 3 hours, again with the 0.05mol/L that contains 0.05%Tween 20, the Tris-HCl damping fluid of pH value 9.1 is washed 3 times, carries out the solid phase time-resolved fluorometry then.The working curve of measuring BSA with this method as shown in Figure 8,3 times of the standard deviation (SD) of the fluorescence signal during with zero-dose (background) are calculated the minimum lower limit that detects that BSA measures, minimum the detecting down that gets this law is limited to 2.0ng/ml, illustrates that this novel titania hybrid nano fluorescent particulate can be used as fluorescence probe and is used for solid phase time-resolved fluorescence biochemistry detection.
Claims (3)
1. nano titania europium fluorescence probe, it is characterized in that: it is to prepare by following operating process, at first form the fluorescence presoma, and then form the hybridized nanometer fluorescent particle with titanate esters generation copolymerization by silylating reagent and trivalent europium-beta-diketone class fluorescence ligand covalent bonding; The monomer of trivalent europium ion, beta-diketon organic ligand and silylating reagent in the described trivalent europium-beta-diketone class fluorescence ligand, the molar ratio between them is 1: 2-3: 5-50, the volume ratio between silylating reagent and titanate esters is 20 μ l:0.85ml;
Described titanate esters is a tetraisopropoxy titanium;
Described silylating reagent is [2-(2-aminoethylamino) ethylamino] propyl trimethoxy silicane;
Described beta-diketon organic ligand is bidentate beta-diketone compounds or four tooth beta-diketone compounds;
The bidentate beta-diketone compounds, structural formula can be expressed as follows:
R in the formula
1=C
6F
5Or fat hydrocarbon substituting group C
nH
2n+1, C
nF
2n+1, n=1,2,3,4 or 5 wherein;
R
2Be the arene substituting group
One of in;
R
3Be chlorosulfonyl (SO
2Cl), different sulphur itrile group (NCS), amino (NH
2) or hydrazine sulfonyl (SO
2NHNH
2);
Four tooth beta-diketone compounds, structural formula can be expressed as follows:
R in the formula
4Be chlorosulfonyl (SO
2Cl), different sulphur itrile group (NCS), amino (NH
2) or hydrazine sulfonyl (SO
2NHNH
2); R
5=C
6F
5Or fat hydrocarbon substituting group C
nH
2n+1, C
nF
2n+1, n=1,2,3,4 or 5 wherein.
2. nano titania europium fluorescence probe according to claim 1, it is characterized in that: the concrete operations of preparation process are, at ambient temperature, with beta-diketon organic ligand and the reaction of silylating reagent generation covalent bond, their consumption mol ratio is 2-3: 5-50, the volumetric molar concentration of beta-diketon organic ligand is 50～500 μ mol/L in the system, makes the fluorescence precursor; Then fluorescence precursor, titanate esters are joined and contain EuCl
3Alcohol-water solution in, stirred down room temperature reaction 24 hours, centrifuging gets final product.
3. nano titania europium fluorescence probe according to claim 2 is characterized in that: described alcohol is ethanol.
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