CN1775898A - Rare earth nanoparticles emitting light based on fluorescence energy transfer principle and preparation method thereof - Google Patents
Rare earth nanoparticles emitting light based on fluorescence energy transfer principle and preparation method thereofDownload PDFInfo
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- CN1775898A CN1775898ACN 200510122716CN200510122716ACN1775898ACN 1775898 ACN1775898 ACN 1775898ACN 200510122716CN200510122716CN 200510122716CN 200510122716 ACN200510122716 ACN 200510122716ACN 1775898 ACN1775898 ACN 1775898A
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Abstract
Description
Technical field
The present invention relates to a kind ofly, be mainly used in the marker detection and the spike of biomolecules, belong to the technical field of biomolecules nanometer marker preparation based on luminous rare-earth nanometer particles of fluorescence energy transfer principle and preparation method thereof.
Background technology
Fluorescent mark and detection technique have in fields such as life science, medical science, immunologys very widely to be used.Yet traditional fluorometric analysis is vulnerable to the interference of non-specific fluorescence.Now the fluorescent marker of Shi Yonging mostly is various organic dye molecules greatly, because its excitation wavelength and emission wavelength are close, Stokes displacement little (20-30nm) is subjected to the interference of exciting light easily during detection.In addition, background fluorescence and scattered light almost cover the scope (350-600nm) of whole fluorescence emission spectrum, will produce non-specific fluorescence and disturb.Photobleaching and quenching effect also take place in traditional organic fluorescence reagent easily, cause fluorescence intensity to reduce.These deficiencies have limited the further raising of this method sensitivity.
Time resolved fluorescence is a kind of more advanced fluorescence analysis method.Its principle is to adopt the rare earth compound of the longer fluorescence transformation period thing of marking, since the Stokes displacement of this marker big (＞150nm) and fluorescence lifetime than high 5～6 orders of magnitude of background material fluorescence lifetime, therefore, as long as delay Measuring Time during mensuration, the signal of measuring marker after the fluorescence for the treatment of the background material is fully decayed again just can be eliminated the interference of various non-specific fluorescences effectively, obtains high sensitivity.Time resolved fluorescence (DELFIA) based on dissolving enhancing principle has obtained using more widely in immunoassay at present.In DEFIA analyzes, after the rare earth inner complex is labeled, need add fluorescence enhancement solution during mensuration dissociates the rare earth ion of mark and discharges, generate the rare earth toughener inner complex that can produce high fluorescent in hydrophobic relatively environment, fluorescence intensity this and the rare earth inner complex that toughener generates has strengthened about 1,000,000 times.The rare earth toughener inner complex that the raising of dissolving enhancing time resolved fluorescence sensitivity for analysis mainly has benefited from high luminous intensity generates.Owing to need to strengthen liquid, this method also is not suitable for solid phase and directly examines and determine, when directly measuring fluorescent signal with the various biomolecules on the rare earth inner complex mark solid phase carrier, fluorescent signal a little less than, sensitivity is not high.Existing time resolved fluorescence technology can not obtain to use in the scope widely.
The nanometer marker is a kind of novel markings thing that development in recent years is got up, because nanoparticle has loaded several fluorescence molecules by 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 existing bibliographical information of this respect has:
The organic high polymer microsphere of doping or surface adsorption, parcel fluorescence molecule.As commercial (BangsLaboratories, Dynal Inc, Molecular Probe etc) polymer microsphere of obtainable various loading dye fluorescence molecules, but most of particle diameter μ m magnitude (＞100nm), the thing that serves as a mark is often excessive, assemble in the aqueous solution easily mutually on hydrophobic surface, and there is leakage in the dye molecule of loading.The nanometer of passing through polymerization preparation in the microemulsion of domestic report is to the micron order polystyrene, polyacrylamide, microballoons such as polyacrylic acid (Zhao Yiqiang, high seapeak, Yang Wuli, the mansion longevity is wide, fluorescently-labeled polymer microsphere and preparation method thereof, patent publication No.: CN1278534A, 2002), 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, the easy photobleaching of fluorescence molecule itself and do not overcome by the serious deficiency of solvent molecule cancellation.
The silicon nano of doping or parcel luminescent dye molecule (Nynke A.M.Verhaegh and Alfonsvan Blaaderen, Langmuir 1994,10,1427-1438; Swadeshmukul Santra, Peng Zhang, Kemin Wang, Rovelyn Tapec, and Weihong Tan, Anal Chem, 2001,73,4988-4993; Tan Weihong, Wang Kemin, Xiao Dan, nm-class core-and-shell particles, patent publication No. CN 1342515A, 2002).With luminescent dye molecule Rhodamine, FITC, Ru (bpy)3Deng luminous kernel, form SiO by polymeric method in microemulsion as nanoparticle2The silicon nano 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 defectives.
The nanoparticle of doping or parcel rare earth compound.As wrap up particle (Jun Feng, Guomin Shan, Angel Maquieira, the Marja E.Koivunen of rare earth oxide or lucium, Bing Guo, Bruce D.Hammock, and Ian M.Kennedy, Anal Chem, 2003,75,5282-5286; 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, publication number CN 1378083A, 2002), since non-solution homogeneous phase preparation, the unicity of this particle, homogeneity, and the dispersiveness in the aqueous solution is still not ideal enough; Particle (Zhiqiang Ye, Mingqian Tan, Guilan Wang, and Jingli Yuan, Anal Chem, 2004,76, the 513-518 of parcel rare earth compounding; Yuan Jingli, Tan Mingqian, Ye Zhiqiang, Wang Guilan, a kind of functional nano rare-earth fluorescent particulate and preparation and application, publication number CN 1493647A, 2004), be the center with luminous strong rare earth compounding, adopt SiO2Be rolled into the nanoparticle thing that serves as a mark, the particle of preparing has 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 to synthesize specially by the multistep organic reaction, the part preparation is complicated, is difficult for obtaining.
The rare-earth fluorescent resonance energy shifts research (P R Selvin and J E Hearst, Proc Natl Acad USA, 1994,91,10024-10028 such as the interaction be mainly used in early days between the molecule, conformational change; P RSelvin, IEEE J Selected Topics in Quantum Elecrtonics, 1996,2,1077-1087).Being used for the detection of biological molecule does not appear in the newspapers as yet.
Summary of the invention
Technical problem: the purpose of this invention is to provide a kind of have the temporal resolution function based on fluorescence energy transfer principle luminous rare-earth nanometer particles and preparation method, eliminate all kinds of interference fluorescence in the common fluorometric analysis by temporal resolution; Obtain the biomolecular labeling thing brighter, that optical property is more stable by nanoparticulate carriers, thereby can carry out the biomolecule detection and the spike of ultra-high sensitive.
Technical scheme: nuclear and SiO that rare-earth fluorescent particle of the present invention is made of rare earth compounding2The shell of parcel constitutes; Promptly this nanoparticle contain a kind of based on the luminous rare earth compounding of fluorescence energy transfer principle as the nuclear of particle with by the shell that form, that be wrapped in nuclear of polyreaction in the microemulsion, but the active function groups of linking probe molecule is contained on the surface of shell.Wherein, rare earth compounding is made up of a kind of sensitization molecule and rare earth ion and a kind of organic ligand with good aqueous solubility as energy donor.
Described rare earth ion is terbium (Tb3+), europium (Eu3+), samarium (Sm3+), dysprosium (Dy3+), a kind of in the ytterbium (Yb), neodymium (Nd), erbium (Er).Described organic ligand is to form high stable constant (stability constant K＞10 with rare earth ion15-20), have binary, the ternary of good aqueous solubility, the multi-carboxy compound of quaternary amine.As diethyl pentetic acid (DTPA), triethyl tetramine six acetate (TTHA), 1,4,8,11-four azepine ten Fourth Rings-1,4,8,11-tetraacethyl (TETA), ethylenediamine tetraacetic acid (EDTA) (EDTA), 1,4,7,10-four azepines 12 ring-N, N ', N ", N tetraacethyl (DOTA) etc.
Sensitization molecule as energy donor is quinoline ketone derivative (Carbostyril), typical compound such as 7-amino-4-methyl-2-copper 8hydroxyquinolate; Coumarins derivative (Coumarin), typical compound such as 7-amino-4-methylcoumarin; Fluoresceins derivative (Fluorescein) is as amino fluorescein; The rhodamine analog derivative is as amino rhodamine B.
The SiO that the shell of parcel luminescent rare earth complexes nuclear is formed by the teos hydrolysis by ammonia-catalyzed in the microemulsion2Constitute SiO2Amino or mercapto functional group are contained in the surface, and the nanoparticle size of generation is at 5-100nm.Microemulsion is the anti-phase system of water-in-oil, and oil phase is a hexanaphthene, and tensio-active agent is Triton X-100 or polyoxyethylene nonylphenol ether (OP-10), and cosurfactant is n-hexyl alcohol or n-Octanol, and water is the aqueous solution that contains luminescent rare earth complexes.The generation of nanoparticle surface functional group is by adding silylating reagent such as the 3-aminopropyl methoxy silane that contains active function groups in the hydrolytic polymerization process, 3-aminopropyl Ethoxysilane (APTES), 3-(2 amino-ethyl ammonia) propyl group-methyl dimethoxysilane etc. is finished.Generate on the shell surface-NH2,-SH functional group can covalently bound various probe molecules such as DNA, antibody, vitamin H, enzyme etc. with the biomolecules of identification and detection or spike correspondence.
Preparation method based on the luminous rare-earth nanometer particles of fluorescence energy transfer principle of the present invention is:
The first step with waiting ammonia carboxylic class organic ligand of reacting weight to be dissolved in respectively in the suitable solvent with the sensitization molecule that has reactive functionality, is mixed afterreaction and is generated the organic ligand that combines the sensitization molecule;
In second step, will wait the rare earth ion nitrate of reacting weight or the aqueous solution of hydrochloride to mix the formation rare earth compounding with the above-mentioned organic ligand that has the sensitization molecule;
The 3rd step, the preparation of rare-earth nanometer particles: after oil phase reagent, tensio-active agent and cosurfactant mixing and stirring, the aqueous solution that adds the rare earth compounding that second step generated, 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 proper amount of acetone centrifugal settling after reaction is finished, to remove reaction soln, separate obtaining SiO through ethanol, water washing2The rare-earth nanometer particles of parcel be suspended in the aqueous solution or dry back standby.The diameter of rare-earth nanometer particles can be controlled by the tetraethoxy mole when of control water and tensio-active agent and the mole dosage of ammoniacal liquor.
Beneficial effect: except that the advantage with temporal resolution function, the advantage of the rare-earth nanometer particles of the present invention's structure is can allow to optimize respectively and rare earth ion bonded organic ligand and sensitization molecule as the rare earth compounding of examining.Because water molecules has the cancellation effect to fluorescence molecule, luminous intensity high with these two character of good water solubility usually be contradiction, its poorly water-soluble of rare earth compounding that many luminous intensities the are high and title complex luminous intensity of good water solubility is not high.A ligand molecular is difficult to have both two kinds of character.The successfully synthetic such part of bibliographical information is arranged at present, is complicated but synthesize.Rare earth compounding of the present invention then can be optimized these two aspects respectively.On the one hand can be by selecting good water solubility, having part that high stable forms constant and make the rare earth compounding that generates have good aqueous solubility and high stability (dissociative do not cooperate rare earth ion concentration low), can select high molar absorption coefficient on the other hand, obtain strong fluorescence as the energy donor molecule, thereby obtain the desirable rare earth part that luminous intensity is high and two kinds of character of good water solubility have both with the sensitization molecule of rare earth ion energy absorption coupling.Employed organic aminocarboxyl chelating agent part and sensitizing agent can have been avoided the complicated organic synthesis of other method synthetic ligands from commercial direct acquisition, and with inexpensive, method is grasped and used easily easily in preparation.The more existing fluorescent marker of nanoparticle tags that obtains has better luminous intensity and optical stability.
Description of drawings
Fig. 1. be the synoptic diagram of rare-earth nanometer particles structure of the present invention.
Fig. 2. the transmission electron microscope picture of the 7-amino of preparation-4-methyl-2-quinolinone-DTPA-Tb nanoparticle.
Fig. 3. the fluorescence and the time resolved fluorescence figure of the 7-amino of preparation-4-methyl-2-quinolinone-DTPA-Tb nanoparticle.
Fig. 4. the time resolved fluorescence figure that supernatant liquor after the 7-amino of preparation-4-methyl-2-quinolinone-abundant centrifugal settling of DTPA-Tb rare-earth nanometer particles and centrifugation are scattered in solution again.The leakage of luminescent ligand compound does not take place in the supernatant liquor fluorescence intensity near the rare earth compounding of background signal intensity explanation parcel.
Embodiment
Embodiment 1: the preparation of 7-amino-4-methyl-2-quinolinone-DTPA-Tb nanoparticle that oligonucleotide probe is modified:
The preparation of the part of rare earth compounding and sensitization molecule conjugate: the 7-amino-4-methyl-2-quinolinone and the diethyl pentetic acid dianhydride of equimolar amount are dissolved in respectively in the anhydrous dimethyl formamide (DMF), add an amount of anhydrous triethylamine and dropwise stir the DMF solution that adds 7-amino-4-methyl-2-quinolinone in diethyl pentetic acid dianhydride DMF solution, reaction is 2 hours under the lucifuge agitation condition.
The preparation of rare earth compounding; Rare earth Tb with equimolar amount3+The aqueous solution (Tb3+Nitrate or hydrochloride) mixed 10 minutes with above-mentioned conjugate solution.
The preparation of rare-earth nanometer particles: with pimelinketone, n-hexyl alcohol, Triton X-100 (v/v, 4: 1: 1) mix 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, after finishing, reaction in milk-white coloured suspension, adds proper amount of acetone centrifugal settling, respectively with ethanol, water washing to remove reaction soln, separate obtaining SiO2The rare-earth nanometer particles of parcel be suspended in the aqueous solution or dry back standby.Fig. 2 is the transmission electron microscope picture of 7-amino-4-methyl-2-quinolinone-DTPA-Tb nanoparticle of making, shows to have favorable uniformity and unicity.Fig. 3 is its fluorescence and time resolution fluorescence spectral figure, and time resolved fluorescence has＞10 times of common intensity of fluorescence and better signal to noise ratio under the similarity condition.The leakage of the luminescent ligand compound that the nanoparticle that the spectrum explanation of Fig. 4 makes does not wrap up has good fluorescent stability.
The preparation of the oligonucleotide probe of rare-earth nanometer particles mark: take by weighing a certain amount of dry surface NH2The rare-earth nanometer particles of modifying is scattered in 1 * PBS solution again, glutaraldehyde (the ultimate density about 1%) solution of adding 25%, reaction is 2 hours under the room temperature, reaction is finished after after the 0.5%Tween-20 washing, the centrifugal supernatant liquor of removing, add the 1 * PBS solution that contains an amount of streptavidin, reaction is 16 hours under the stirring at room, after reaction is finished, 0.5%Tween-20 1 * PBS solution washing, 1 * PBS solution of adding capacity Biotin-oligo after the centrifugation, reaction is 3 hours under the room temperature, after reaction is finished, be suspended in 1 * PBS solution for standby behind 31 * PBS solution washings.
Embodiment 2: the preparation of amino fluorescein-DTPA-Yb nanoparticle:
The preparation of the part of rare earth compounding and sensitization molecule conjugate: the amino fluorescein and the diethyl pentetic acid dianhydride of equimolar amount are dissolved in respectively in the anhydrous dimethyl formamide (DMF), add an amount of anhydrous triethylamine and dropwise stir the DMF solution that adds amino fluorescein in diethyl pentetic acid dianhydride DMF solution, reaction is 2 hours under the lucifuge agitation condition.
The preparation of rare earth compounding: with the Rare Earth Y b of equimolar amount3+The aqueous solution (Yb3+Hydrochloride) mixed 10 minutes with above-mentioned conjugate solution.
The preparation of rare-earth nanometer particles: with pimelinketone, n-hexyl alcohol, Triton X-100 (v/v, 4: 1: 1) mix 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, after finishing, reaction in milk-white coloured suspension, adds proper amount of acetone centrifugal settling, respectively with ethanol, water washing to remove reaction soln, separate obtaining SiO2The rare-earth nanometer particles of parcel be suspended in the aqueous solution or dry back standby.
The preparation of embodiment 3:7-amino-4-methyl-2-quinolinone-TTHA-Eu nanoparticle:
The preparation of the part of rare earth compounding and sensitization molecule conjugate: triethyl tetramine six acetate (TTHA) of certain molar weight are dissolved in the anhydrous dimethyl formamide (DMF), and add a small amount of anhydrous triethylamine, agitation condition reacted 12 hours down.The DMF solution of the isobutyl chlorocarbonate of equimolar amount is dropwise stirred down to add in the above-mentioned mixed solution, reacts the DMF solution that adds the 7-amino-4-methyl-2-quinolinone of equimolar amount after 30 minutes, and reaction is 5 hours under the lucifuge agitation condition.
The preparation of rare earth compounding: with the rare earth Eu of equimolar amount3+The aqueous solution (Eu3+Hydrochloride) mixed 10 minutes with above-mentioned conjugate solution.
The preparation of rare-earth nanometer particles: with pimelinketone, n-hexyl alcohol, Triton X-100 (v/v, 4: 1: 1) mix 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, after finishing, reaction in milk-white coloured suspension, adds proper amount of acetone centrifugal settling, respectively with ethanol, water washing to remove reaction soln, separate obtaining SiO2The rare-earth nanometer particles of parcel be suspended in the aqueous solution or dry back standby.
Claims (10)
1. one kind based on the luminous rare-earth nanometer particles of fluorescence energy transfer principle, it is characterized in that this nanoparticle contain a kind of based on the luminous rare earth compounding of fluorescence energy transfer principle as the nuclear of particle with by the shell that form, that be wrapped in nuclear of polyreaction in the microemulsion, but the active function groups of linking probe molecule is contained on the surface of shell, wherein, rare earth compounding is made up of a kind of sensitization molecule and rare earth ion and a kind of organic ligand with good aqueous solubility as energy donor.
2. according to claim 1 based on the luminous rare-earth nanometer particles of fluorescence energy transfer principle, it is characterized in that described rare earth ion is terbium " Tb3+", europium " Eu3+", samarium " Sm3+", dysprosium " Dy3+", a kind of in the ytterbium " Yb ", neodymium " Nd ", erbium " Er ".
3. according to claim 1 based on the luminous rare-earth nanometer particles of fluorescence energy transfer principle, it is characterized in that described organic ligand is can form the high stable constant with rare earth ion, have containing of good aqueous solubility a plurality of amino and the ammonia carboxylic class organic molecule of carboxyl.
4. according to claim 3 a kind of based on the luminous rare-earth nanometer particles of fluorescence energy transfer principle, it is characterized in that described ammonia carboxylic class organic molecule is diethyl pentetic acid " DTPA ", triethyl tetramine six acetate " TTHA ", 1,4,8,11-four azepine ten Fourth Rings-1,4,8,11-tetraacethyl " TETA ", ethylenediamine tetraacetic acid (EDTA) " EDTA ", 1,4,7,10-four azepines 12 ring-N, N ', N ", a kind of in the N tetraacethyl " DOTA ".
5. according to claim 1 a kind of based on the luminous rare-earth nanometer particles of fluorescence energy transfer principle, it is characterized in that, sensitization molecule as energy donor is quinoline ketone derivative " Carbostyril ", or coumarins derivative " Coumarin ", or fluoresceins derivative " Fluorescein ", or rhodamine analog derivative.
6. according to claim 5 a kind of based on the luminous rare-earth nanometer particles of fluorescence energy transfer principle, it is characterized in that, be 7-amino-4-methyl-2-copper 8hydroxyquinolate as the sensitization molecule of energy donor, 7-amino-4-methylcoumarin, amino fluorescein, a kind of in the amino rhodamine B.
7. according to claim 1 based on the luminous rare-earth nanometer particles of fluorescence energy transfer principle, it is characterized in that wrapping up the SiO that the shell of luminescent rare earth complexes nuclear is formed by the teos hydrolysis by ammonia-catalyzed in the microemulsion2Constitute SiO2Amino or mercapto functional group can be contained in the surface, and the nanoparticle size of generation is at 5-100nm.
8. according to claim 1 or 7 described based on the luminous rare-earth nanometer particles of fluorescence energy transfer principle, it is characterized in that microemulsion is the anti-phase system of water-in-oil, oil phase is a hexanaphthene, tensio-active agent is Triton X-100 or polyoxyethylene nonylphenol ether (OP-10), cosurfactant is n-hexyl alcohol or n-Octanol, and water is the aqueous solution that contains luminescent rare earth complexes.
9. according to claim 1ly it is characterized in that, but to contain the active function groups of linking probe molecule be by containing-HN on the surface of shell based on the luminous rare-earth nanometer particles of fluorescence energy transfer principle2Or-hydrolysis of the silanizing agent of SH or to SiO2Generation is modified on the surface, can discern and detect corresponding biomolecules by the various probe molecules on functional group's covalent modification such as DNA, antibody, vitamin H, enzyme etc., or is used for mark and spike biomolecules by the chemical coupling of surface functional group.
10. preparation method based on the luminous rare-earth nanometer particles of fluorescence energy transfer principle as claimed in claim 1 is characterized in that the method for preparing is:
The first step with waiting ammonia carboxylic class organic ligand of reacting weight to be dissolved in respectively in the suitable solvent with the sensitization molecule that has reactive functionality, is mixed afterreaction and is generated the organic ligand that combines the sensitization molecule;
In second step, will wait the rare earth ion nitrate of reacting weight or the aqueous solution of hydrochloride to mix the formation rare earth compounding with the above-mentioned organic ligand that has the sensitization molecule;
The 3rd step, the preparation of rare-earth nanometer particles: after oil phase reagent, tensio-active agent and cosurfactant mixing and stirring, the aqueous solution that adds the rare earth compounding that second step generated, 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 proper amount of acetone centrifugal settling after reaction is finished, to remove reaction soln, separate obtaining SiO through ethanol, water washing2The rare-earth nanometer particles of parcel be suspended in the aqueous solution or dry back standby.
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