CN101486903B - Preparation of rare earth luminous nanoparticle based on pyridine dicarboxylic acid - Google Patents
Preparation of rare earth luminous nanoparticle based on pyridine dicarboxylic acid Download PDFInfo
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Abstract
The invention relates to a preparation method of rare-earth luminescent nanometer particles based on pyridine dicarboxylic acid. The rare-earth luminescent nanometer particle comprises SiO2 coating luminescent rare-earth composition; the rare-earth composition is produced by ligand pyridine dicarboxylic acid combined with rare-earth ions; and SiO2 nanometer particles with active functional group on the surface are formed by the polymerization reaction of the rare-earth composition in the microemulsion and the silanization. The prepared rare-earth luminescent nanometer particle has high luminous intensity and good water solubility, and can be used for a variety of time-resolved fluorescence analysis and imaging. Compared with the homogeneous rare-earth nanometer particle preparation method, the preparation method has the advantages of low preparation cost and simple method, and can be widely applied.
Description
Technical field
The present invention relates to a kind of preparation method of the rare earth luminous nanoparticle based on pyridine dicarboxylic acid, be mainly used in the fluoroscopic examination and the spike of biomolecules, belong to the technical field of biomolecules nanometer affinity tag preparation.
Background technology
Fluoroscopic examination, imaging technique have a wide range of applications in various fields such as life science, medical science; Yet the various organic dye molecules that traditional fluorometric analysis is used are vulnerable to the interference (exciting light, scattered light and analyte background fluorescence) of various non-specific fluorescences, and photobleaching takes place the while dye molecule easily and quenching effect causes fluorescence intensity to reduce.The nanometer affinity tag is a kind of novel markings thing that development in recent years is got up; Because nanoparticle has loaded several fluorescence molecules through modes such as surface adsorption or embeddings; Therefore with behind the nanometer particle to mark, fluorescent emission intensity will strengthen greatly, the sensitivity that strong lifting is measured.
The preparation method of relevant fluorescent nano particles report commercial (Bangs Laboratories arranged; DynalInc; Molecular Probe etc) polymer microsphere of obtainable various loading dye fluorescence molecules, but most of polymer microsphere particle diameter μ m magnitude (＞100nm), the thing size that serves as a mark is often excessive; Assemble in the aqueous solution easily each other on hydrophobic surface, and there is leakage in the dye molecule of loading.Domestic report is crossed through polyreaction in the microemulsion and is prepared method (Chinese patent publication number CN1278534A, 2002 year, the Zhao Yiqiang of nanometer to microballoons such as micron-sized PS, polyacrylamide, ROHM; High seapeak; Yang Wuli, the mansion longevity is wide, fluorescently-labeled polymer microsphere and preparation method thereof); The surface adsorption of these microballoons or covalent bonding a plurality of FITC, Rhodamine 6G, Cy fluorochrome molecule; Owing to be to carry fluorescence molecule at microsphere surface, fluorescence molecule itself is prone to be subject to by photobleaching with in the aqueous solution deficiency of solvent molecule cancellation, is not overcome.
Bibliographical information SiO
2The parcel fluorescence molecule prepares method (Nynke A.M.Verhaeghand Alfons van Blaaderen, Langmuir, 1994,10, the 1427-1438 of nanoparticle; Swadeshmukul Santra, Peng Zhang, Kemin Wang, Rovelyn Tapec and Weihong Tan, Anal Chem, 2001,73,4988-4993; Swadeshmukul Santra, Heesun Yang, Debamitra Dutta, Jessie T.Stanley, Paul H.Holloway; Weihong Tan, Brij M.Moudgilb and Robert A.Mericle, ChemCommun, 2004; 2810-2811), Chinese patent publication number CN 1342515A,, Tan Weihong in 2002; Wang Kemin, Xiao Dan, nm-class core-and-shell particles discloses the nanoparticle preparation method who wraps up fluorescent substance.More than these methods with luminescent dye molecule Rhodamine, FITC, Ru (bpy)
3Deng luminous kernel, form SiO through polymeric method in microemulsion as nanoparticle
2The fluorescent nano particles of parcel.This nanoparticle tags possess hydrophilic property, surface are modified easily, and compare with fluorescence molecule and to have better optical stability and brightness.Still do not overcome but fluorescence molecule inherent Stokes displacement is little, be subject to various non-specific fluorescence interferential deficiencies.
Have some unique advantages with rare earth compound as fluorescent marker, far away apart like emission wavelength and excitation wavelength, the Stokes displacement can reach more than the 150nm; Fluorescence emission peak is narrow, often less than 10nm; Fluorescence lifetime is long; Can reach Millisecond; Than high 5～6 one magnitude of fluorescence lifetime of general background material, therefore can carry out the time resolved fluorescence analysis through fluorescence delay measurements technology, the interference of eliminating various non-specific fluorescences effectively obtains high sensitivity and fluoroscopic image more clearly.Then gathered the advantage of rare earth compound and nanoparticle with the nanoparticle of rare earth compound preparation, comprised many light emitting molecules and had higher fluorescence intensity.Integument has avoided environmental factors (solvent molecule, oxygen) to the cancellation effect of fluorescence and be more prone to modify probe molecule.
The preparation document of relevant rare-earth nanometer particles (Jun Feng, Guomin Shan, Angel Maquieira; Marja E.Koivunen, Bing Guo, Bruce D.Hammock and Ian M.Kennedy; Anal Chem; 2003,75,5282-5286) reported a kind of nanoparticle preparation method who wraps up rare earth oxide; Chinese patent publication number CN 1378083A, 2002, Sun Baoquan, clothing light Shun; Chen Depiao, Zhao Shuying, Zhou Yuxiang; Cheng Jing is used for rare-earth nanometer particles, the Preparation Method And The Use of biological material label, discloses a kind of method of wrapping up the particle preparation of lucium.Because these methods are used the preparation of non-solution homogeneous phase, the homogeneity of prepared particle shape, the controllability of size, dispersed not ideal enough in the aqueous solution.
Chinese patent publication number CN 1493647A, 2004, Yuan Jingli; Tan Mingqian, Ye Zhiqiang, Wang Guilan; A kind of functional nano rare-earth fluorescent particulate and preparation and application; Disclose a kind of particle preparation method of wrapping up rare earth compounding, its method is to be the center with luminous strong rare earth compounding, adopts SiO
2Be rolled into the nanoparticle thing that serves as a mark; The particle of preparing has favorable uniformity and stronger fluorescence intensity; Can be used for the time resolved fluorescence analysis, but the part of the rare earth compounding that uses does not have commercial source, need through the multistep organic reaction synthetic specially; The part preparation is complicated, is difficult for obtaining.
Chinese patent publication number CN 1775898A, 2006, Chen Yang; Based on fluorescence energy transfer principle luminous rare-earth nanometer particles and preparation method, a kind of particle preparation method of wrapping up rare earth compounding is disclosed, its method is to prepare water miscible rare earth compounding through sensitization molecular fluorescence enhanced method; Prepared rare earth compounding luminous intensity is high; Good water solubility, synthesis material has commercial source, easily preparation.The particle of preparing has favorable uniformity and strong fluorescence intensity.
Pyridine dicarboxylic acid and rare earth ion can generate has the very rare earth compounding of hyperfluorescence intensity, once is used to measure content (Ci Yunxiang, Ning Minzhu, Yang Fangying, SCI, 1983,4 (1), the 115-118 of rare earth ion Tb, Eu, Dy; Tan Peigong, Li Lanying, Huang Hanguo, assay office, 1993,12 (5), 44-46).The title complex of using pyridine dicarboxylic acid and rare earth ion formation prepares luminescent nanoparticle and is used to detect various biomolecules and does not appear in the newspapers as yet both at home and abroad.Prepare SiO through the solution homogeneous reaction
2The key of rare-earth nanometer particles of parcel is synthetic rare earth compounding with good aqueous solubility, stability, high luminous intensity, and at present such rare earth compounding kind seldom and needs complicated organic synthesis, and cost is expensive, is difficult for obtaining.
Summary of the invention
Technical problem: the preparation method who the purpose of this invention is to provide a kind of rare earth luminous nanoparticle based on pyridine dicarboxylic acid; Be a kind of complicated preparation method who synthesizes and use expensive feedstock production rare earth luminous nanoparticle that need not; High, the good water solubility of rare-earth nanometer particles luminous intensity based on the preparation of pyridine dicarboxylic acid method can be used for various time resolved fluorescence analyses and imaging.
Technical scheme: the present invention realizes through following technical scheme: as light emitting molecule, form SiO through polyreaction in the microemulsion with rare earth compounding
2The nanoparticle of parcel rare earth compounding, but the surface of nanoparticle has the active function groups of linking probe molecule, is used for the fluoroscopic examination and the imaging of biomolecules, and light emitting molecule is the title complex that pyridine dicarboxylic acid and rare earth ion generate.
Described rare earth ion is terbium ion (Tb
3+), europium ion (Eu
3+), samarium ion (Sm
3+), dysprosium ion (Dy
3+) in a kind of.
The part that generates title complex with rare earth ion is a pyridine-2, the 6-dicarboxylicacid, and promptly two carboxyl substituents are to be connected in 2 and 6 of pyridine ring respectively.
Pyridine-2, the 6-dicarboxylicacid
Pyridine-2,6-dicarboxylicacid (DPA) and rare earth ion (Ln
3+) title complex that generates is Ln (DPA)
3Or Ln (DPA)
2Or a kind of in Ln (DPA) the type title complex.
Concrete step is:
The first step is pressed 1: 3 mixed in molar ratio reaction formation rare earth compounding with the aqueous solution and the pyridine dicarboxylic acid solution of rare earth ion nitrate salt or hydrochloride;
Second step; The preparation of rare-earth nanometer particles: in the water-in-oil reverse microemulsion liquid system; After oil phase reagent, tensio-active agent and cosurfactant mixing and stirring; The aqueous solution that adds the rare earth compounding that the first step generates, fully stir form water in oil microemulsion after, add the reaction that is hydrolyzed of tetraethoxy and ammoniacal liquor; In hydrolysis reaction or after the reaction, add silylating reagent and continue reaction, in milk-white coloured suspension, add acetone centrifugal settling after reaction is accomplished, to remove reaction soln, spinning obtains SiO through ethanol, water washing
2The rare-earth nanometer particles of parcel be suspended in the aqueous solution or dry back subsequent use.
Oil phase is a hexanaphthene in the water-in-oil reverse microemulsion liquid system, and tensio-active agent is Triton X-100 or polyoxyethylene nonylphenol (OP-10), and cosurfactant is n-hexyl alcohol or n-Octanol, and water is the aqueous solution that contains luminescent rare earth complexes.
The SiO that prepared rare-earth nanometer particles is formed by ammonia-catalyzed teos hydrolysis in the water-in-oil reverse microemulsion liquid system
2Constitute.
The active function groups on prepared rare-earth nanometer particles surface generates through in microemulsion, adding the silylating reagent that has different activities functional group; Silylating reagent is an aminosilane reagent; Or hydrosulphonyl silane reagent; Or 3-glycidyl ether oxygen propyl silylating reagent, these active function groups can further covalently bound various probe molecule such as DNA, antibody, vitamin H, enzyme etc. with identification and detection or the corresponding biomolecules of spike.
Beneficial effect: at present the rare earth compounding kind with good aqueous solubility, stability, high luminous intensity of bibliographical information seldom, part preparation needs complicated organic synthesis, cost is expensive, is difficult for acquisition.Rare earth part pyridine-2 of the present invention, 6-dicarboxylicacid and rare earth ion Tb, Eu, Dy, Sm can both generate fluorescence complex, and fluorescence intensity is strong, and general part can only generate the title complex with certain water miscible enough hyperfluorescences with Eu, Tb ion usually.Pyridine-2; The title complex that 6-dicarboxylicacid and rare earth ion generate has good water-solubility and stability; Owing to good water solubility, can make the nanoparticle of more highly doped light emitting molecule concentration, have high luminous intensity and can be applied to the long fluorescence lifetime that time resolved fluorescence is analyzed.Employed part pyridine dicarboxylic acid can be from commercial acquisition; Low price; Compare with previous rare-earth nanometer particles preparation method, avoided the complicated organic synthesis of synthetic ligands, preparation cost reduces greatly; Method is simpler, helps the rare earth nano affinity tag to be employed in field widely.
Description of drawings
Fig. 1. the transmission electron microscope picture of pyridine dicarboxylic acid-Eu nanoparticle.
Fig. 2. the time resolution fluorescence spectral figure of pyridine dicarboxylic acid-Eu nanoparticle.
Fig. 3. the transmission electron microscope picture of pyridine dicarboxylic acid-Tb nanoparticle.
Fig. 4. the time resolution fluorescence spectral figure of pyridine dicarboxylic acid-Tb nanoparticle.
Fig. 5. the time resolution fluorescence spectral figure of pyridine dicarboxylic acid-Dy nanoparticle.
Embodiment
Rare-earth nanometer particles is by SiO
2The parcel luminescent rare earth complexes constitutes; Rare earth compounding combines rare earth ion to generate by the part pyridine dicarboxylic acid; SiO
2The parcel rare earth compounding forms SiO through the hydrolysis of ammonia-catalyzed tetraethoxy in the water-in-oil reverse micro emulsion
2Generate.The diameter of rare-earth nanometer particles can be controlled through the tetraethoxy mole when of control water and tensio-active agent and the mole dosage of ammoniacal liquor.The nanoparticle size that generates is usually at 10-150nm.In the hydrolytic polymerization process, use the silylating reagent that has different activities functional group, can be at SiO
2The surface generates different activity functional group respectively, like silylating reagent 3-aminopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, the 3-glycidyl ether oxygen propyl trimethoxy silicane can be at SiO
2The surface generates respectively-NH
2,-SH, 3-glycidyl ether oxygen propyl functional group, these functional groups can further covalently bound various probe molecule such as DNA, antibody, vitamin H, enzyme etc. with identification and detection or the corresponding biomolecules of spike.
Embodiment 1: the preparation of pyridine dicarboxylic acid-Eu nanoparticle that oligonucleotide probe is modified
The preparation of rare earth compounding: with rare earth Eu
3+The aqueous solution (Eu
3+Hydrochloride) with pyridine dicarboxylic acid solution by 1: 3 mixed in molar ratio reaction 10 minutes.
The preparation of rare-earth nanometer particles: pimelinketone, n-hexyl alcohol, Triton X-100 (v/v, 4: 1: 1) are mixed and stir, add an amount of rare earth compounding solution (water); After fully stirring the formation water-in-oil microemulsion; Add tetraethoxy and strong aqua, stir after 2 hours, add aminopropyl triethoxysilane (aminosilane reagent); Reaction mixture under agitation reacted 20 hours; Back adding proper amount of acetone centrifugal settling in milk-white coloured suspension is accomplished in reaction, respectively with ethanol, water washing to remove reaction soln, spinning obtains SiO
2The rare-earth nanometer particles of parcel be suspended in the aqueous solution or dry back subsequent use, Fig. 1 is the transmission electron microscope picture of pyridine dicarboxylic acid-Eu nanoparticle of making, shows to have favorable uniformity and unicity.Fig. 2 is the time resolution fluorescence spectral figure of pyridine dicarboxylic acid-Eu nanoparticle.
The preparation of the oligonucleotide probe of rare-earth nanometer particles mark: take by weighing a certain amount of dry surface NH
2The rare-earth nanometer particles of modifying is scattered in 1 * PBS solution again, adds 25% LUTARALDEHYDE (ultimate density about 1%) solution, and reaction is 2 hours under the room temperature; Reaction is accomplished after after the 0.5%Tween-20 washing, the centrifugal supernatant of removing adds the 1 * PBS solution that contains an amount of streptavidin; Reaction is 16 hours under the stirring at room, after reaction is accomplished, with the 1 * PBS solution washing that contains 0.5%Tween-20; 1 * PBS the solution that adds capacity Biotin-oligo after the spinning, reaction is 3 hours under the room temperature, after reaction is accomplished; With 1 * PBS solution washing 3 times, the oligonucleotides-modified nanoparticle in washing back is suspended in 1 * PBS solution subsequent use.
Embodiment 2: the preparation of pyridine dicarboxylic acid-Tb nanoparticle
The preparation of rare earth compounding: with rare earth Tb
3+The aqueous solution (Tb
3+Nitrate salt or hydrochloride) with pyridine dicarboxylic acid solution by 1: 3 mixed in molar ratio reaction 10 minutes.
The preparation of rare-earth nanometer particles: pimelinketone, n-hexyl alcohol, Triton X-100 (v/v, 4: 1: 1) are mixed and stir, add an amount of rare earth compounding solution (water); After fully stirring the formation water-in-oil microemulsion; Add tetraethoxy and strong aqua, stir after 2 hours, add aminopropyl triethoxysilane (silylating reagent); Reaction mixture under agitation reacted 20 hours; Back adding proper amount of acetone centrifugal settling in milk-white coloured suspension is accomplished in reaction, respectively with ethanol, water washing to remove reaction soln, spinning obtains SiO
2The rare-earth nanometer particles of parcel be suspended in the aqueous solution or dry back subsequent use.Fig. 3 is the transmission electron microscope picture of pyridine dicarboxylic acid-Tb nanoparticle of making.Fig. 4 is its time resolution fluorescence spectral figure.
Embodiment 3: the preparation of pyridine dicarboxylic acid-Dy nanoparticle
The preparation of rare earth compounding: with rare earth Dy
3+The aqueous solution (Dy
3+Hydrochloride) with pyridine dicarboxylic acid solution by 1: 3 mixed in molar ratio reaction 10 minutes.
The preparation of rare-earth nanometer particles: pimelinketone, n-hexyl alcohol, Triton X-100 (v/v, 4: 1: 1) are mixed and stir, add an amount of rare earth compounding solution (water); After fully stirring the formation water-in-oil microemulsion; Add tetraethoxy and strong aqua, stir after 2 hours, add aminopropyl triethoxysilane (silylating reagent); Reaction mixture under agitation reacted 20 hours; Back adding proper amount of acetone centrifugal settling in milk-white coloured suspension is accomplished in reaction, respectively with ethanol, water washing to remove reaction soln, spinning obtains SiO
2The rare-earth nanometer particles of parcel be suspended in the aqueous solution or dry back subsequent use.Fig. 5 is the time resolution fluorescence spectral figure of pyridine dicarboxylic acid-Dy nanoparticle of making.
Claims (8)
1. the preparation method based on the rare earth luminous nanoparticle of pyridine dicarboxylic acid is characterized in that with rare earth compounding as light emitting molecule, through polyreaction formation SiO in the microemulsion
2The nanoparticle of parcel rare earth compounding, but the surface of nanoparticle has the active function groups of linking probe molecule, is used for the fluoroscopic examination and the imaging of biomolecules, and light emitting molecule is the title complex that pyridine dicarboxylic acid and rare earth ion generate.
2. the preparation method of a kind of rare earth luminous nanoparticle based on pyridine dicarboxylic acid according to claim 1 is characterized in that the concrete step of preparation method is:
The first step is pressed 1: 3 mixed in molar ratio reaction formation rare earth compounding with the aqueous solution and the pyridine dicarboxylic acid solution of rare earth ion nitrate salt or hydrochloride;
Second step; The preparation of rare-earth nanometer particles: in the water-in-oil reverse microemulsion liquid system; After oil phase reagent, tensio-active agent and cosurfactant mixing and stirring; The aqueous solution that adds the rare earth compounding that the first step generates, fully stir form water in oil microemulsion after, add the reaction that is hydrolyzed of tetraethoxy and ammoniacal liquor; In hydrolysis reaction or after the reaction, add silylating reagent and continue reaction, in milk-white coloured suspension, add acetone centrifugal settling after reaction is accomplished, to remove reaction soln, spinning obtains SiO through ethanol, water washing
2The rare-earth nanometer particles of parcel be suspended in the aqueous solution or dry back subsequent use.
3. the preparation method of a kind of rare earth luminous nanoparticle based on pyridine dicarboxylic acid according to claim 1 is characterized in that described rare earth ion is a kind of in terbium ion, europium ion, samarium ion, the dysprosium ion.
4. the preparation method of a kind of rare earth luminous nanoparticle based on pyridine dicarboxylic acid according to claim 1 and 2; The part that it is characterized in that generating with rare earth ion title complex is a pyridine-2; The 6-dicarboxylicacid, promptly two carboxyl substituents are to be connected in 2 and 6 of pyridine ring respectively.
5. the preparation method of a kind of rare earth luminous nanoparticle based on pyridine dicarboxylic acid according to claim 1 is characterized in that pyridine dicarboxylic acid " DPA " and rare earth ion " Ln
3+" title complex that generates is Ln (DPA)
3Or Ln (DPA)
2Or a kind of in Ln (DPA) the type title complex.
6. the preparation method of a kind of rare earth luminous nanoparticle based on pyridine dicarboxylic acid according to claim 2; It is characterized in that oil phase is a hexanaphthene in the water-in-oil reverse microemulsion liquid system; Tensio-active agent is TritonX-100 or polyoxyethylene nonylphenol; Cosurfactant is n-hexyl alcohol or n-Octanol, and water is the aqueous solution that contains luminescent rare earth complexes.
7. the preparation method of a kind of rare earth luminous nanoparticle based on pyridine dicarboxylic acid according to claim 2 is characterized in that the SiO that prepared rare-earth nanometer particles is formed by ammonia-catalyzed teos hydrolysis in the water-in-oil reverse microemulsion liquid system
2Constitute.
8. the preparation method of a kind of rare earth luminous nanoparticle based on pyridine dicarboxylic acid according to claim 2; The active function groups that it is characterized in that prepared rare-earth nanometer particles surface generates through in microemulsion, adding the silylating reagent that has different activities functional group; Silylating reagent is an aminosilane reagent; Or hydrosulphonyl silane reagent; Or 3-glycidyl ether oxygen propyl silylating reagent, these active function groups can further covalently bound various probe molecule DNA, antibody, vitamin H, enzyme is with identification and detection or the corresponding biomolecules of spike.
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