CN104371728B - Conversion nano granule and preparation method thereof on a kind of folacin coupled water solublity - Google Patents
Conversion nano granule and preparation method thereof on a kind of folacin coupled water solublity Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 82
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 title claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000008187 granular material Substances 0.000 title claims abstract description 36
- 235000019152 folic acid Nutrition 0.000 title claims abstract description 33
- 239000011724 folic acid Substances 0.000 title claims abstract description 33
- 229940064302 folacin Drugs 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 21
- 238000004020 luminiscence type Methods 0.000 claims abstract description 16
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229960000304 folic acid Drugs 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005642 Oleic acid Substances 0.000 claims abstract description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000018199 S phase Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 36
- 125000003368 amide group Chemical group 0.000 claims description 19
- 229920000587 hyperbranched polymer Polymers 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 229960004756 ethanol Drugs 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 11
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 6
- WCZAXBXVDLKQGV-UHFFFAOYSA-N n,n-dimethyl-2-(7-oxobenzo[c]fluoren-5-yl)oxyethanamine oxide Chemical compound C12=CC=CC=C2C(OCC[N+](C)([O-])C)=CC2=C1C1=CC=CC=C1C2=O WCZAXBXVDLKQGV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 238000003384 imaging method Methods 0.000 abstract description 5
- 206010028980 Neoplasm Diseases 0.000 abstract description 4
- 201000011510 cancer Diseases 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000008685 targeting Effects 0.000 abstract description 3
- 229910004064 NOBF4 Inorganic materials 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 7
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- -1 rare earth ion Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003929 folic acid group Chemical group 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910002319 LaF3 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
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- 238000002161 passivation Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000009870 specific binding Effects 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
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Abstract
The invention discloses conversion nano granule and preparation method thereof on a kind of folacin coupled water solublity, synthesize the up-conversion luminescence nano-particle UCNPs of six side's phases initially with high temperature thermal decomposition method, then adopt Tetrafluoroboric acid nitrous NOBF4Process UCNPs, replace the oleic acid molecular on its surface, then react with hydrophilic dissaving polymer, obtain conversion nano granule on the water solublity that dissaving polymer is modified, finally react with folic acid, obtain conversion nano granule on folacin coupled water solublity.On folacin coupled water solublity prepared by the present invention, conversion nano granule has the advantages such as good dispersion, biocompatibility and targeting, can be used for the targeted imaging of cancer cell.
Description
Technical field
The present invention relates to conversion nano granule and preparation method thereof on a kind of folacin coupled water solublity, belong to field of nanometer material technology.
Background technology
Rare earth up-conversion luminescent material Up-conversion(UC) it is a kind of luminescent material sending visible ray under near infrared light excites, by multi-photon mechanism, long-wave radiation can be converted to shortwave radiation.This material emission runs counter to Stokes law, and be therefore otherwise known as anti-Stokes law luminescent material.UC luminescence is based on the interelectric transition of rare earth element 4f.Luminescence process can be divided into three steps: 1. parent lattice absorbs excitation energy；2. parent lattice by absorb spectroscope properties to excited ion so that it is excite；3. the rare earth ion being excited sends fluorescence and returns substrate.Upper transformation process mainly has the transmission of Excited-state Absorption, energy, two-photon absorption and four kinds of forms of photon avalanches.
Rare earth luminescent material mainly has the compositions such as host material, activator (centre of luminescence), coactivator and sensitizer.The efficiency of up-conversion luminescence depends greatly on the host material of conversion.Host material itself is not luminous, but can provide suitable crystalline field for active ions so that it is produce suitable transmitting.The general requirement that selects of host material has the lattice matched with dopant ion, good chemical stability and relatively low lattice vibration phonon energy etc..Difference according to matrix material component, it is possible to the substrate of up-conversion luminescent material is broadly divided into oxide, halogenide and sulfide etc..YF3、LaF3、NaYF4And LiYF4It is all extraordinary substrate Deng material, under near infrared light excites, launches visible ray or even ultraviolet light.
Up-conversion luminescence nanomaterial (upper conversion nano granule) has high chemical stability, excellent light stability, narrow band gap transmitting, there is stronger tissue penetration under near-infrared laser excites, to biological tissue's not damaged, without the interference of background fluorescence, have a wide range of applications in biomedical etc., such as bio-imaging, biological detection, multi-modality imaging, cancer optical dynamic therapy, medicine carrying etc..Additionally, except the application at above-mentioned biological field is extensively concerned, abiotic field (as optical information store, 3D shows, safety anti-fake and solaode etc.) also have good application prospect.
Up to the present, in synthesis, the method for conversion nano granule mainly has precipitation/coprecipitation, hydrothermal/solvent full-boiled process, pyrolysis method, sol-gel process and self-propagating combustion etc..But these methods obtain oil-soluble upper conversion nano granule, its water solublity and poor biocompatibility mostly, limit its application in fields such as biomedicines, therefore need after synthesis nano-particle, its surface to be modified.The method of conventional finishing mainly has surface passivation, surface ligand oxidizing process, surface ligand exchange process, polymer wrapped method, coated with silica method, electrostatic attraction layer-layer to assemble cladding process (LBL) etc..Simultaneously in order to further upper conversion nano granule is applied in imaging, it is necessary step to upper conversion nano particle surface functionalization.At present, upper conversion nano particle surface often contains-COOH ,-NH2Or MA, then can link biomolecule further, such as folic acid, peptide, albumen, DNA etc..
Cancer cell surface is many a lot of folacin receptors than normal cell, and folic acid can specific recognition be combined with folacin receptor, therefore, folacin receptor can produce specific binding with folacin coupled upper conversion nano granule, and by upper conversion nano particle transport to cell, under 980nm excites, send fluorescence, it is achieved that targeting recognition detection.The way of conventional folacin coupled upper conversion nano granule is first with conversion nano granule in PEI cladding, then passes through EDC and NHS and is obtained by reacting, and process is complicated, and cost is high.Such as first folic acid activated by Chinese invention patent CN201410169902.8, it is then added in cysteine-modifying rare earth upconversion nano crystal aqueous dispersions, and react the regular hour when normal temperature and pressure lucifuge, form the nanocrystalline of modified with folic acid, finally, it is isolated purification, namely obtains the water-solubility rare-earth up-conversion luminescence nanometer crystal of modified with folic acid.Its Folic Acid activation step is folic acid, EDC, NHS to be reacted when lucifuge.
Summary of the invention
The present invention is directed to above-mentioned deficiency, be prepared for conversion nano granule on a kind of folacin coupled water solublity.
The technical scheme is that:
(1) by Y (CF that total amount of substance is 1mmol3COO)3、Yb(CF3COO)3、Er(CF3COO)3Or Tm (CF3COO)3, 10mmol sodium fluoride and the mixed organic solvents that is made up of 10mL oleic acid and 10mL carbon octadecylene join in 50mL three-neck flask and be heated to 120 DEG C; it is continually fed into nitrogen protection and heats 1h; then 320 DEG C and magnetic agitation 1h are risen to the heating rate of 1 ° of C/min; naturally cool to room temperature; add dehydrated alcohol; it is centrifuged and is precipitated, more repeatedly by water and washing with alcohol, finally give the upper conversion nano granule that may be dissolved in hexamethylene and hexane.
(2) by the 5mL Tetrafluoroboric acid nitrous NOBF of the 5mL up-conversion luminescence nano-particle hexane dispersion soln of 1-5g/L Yu 0.1-0.6g/L4Dichloromethane solution at room temperature mixes, and is shaken gently for by mixture, until upper conversion nano particle precipitation, is then centrifuged for separating, removes supernatant.
(3) the up-conversion luminescence nano-particle obtained in step 2 is scattered in water again, 1:1-1:10 by volume, add the Hyperbranched Polymer with Terminal Amido aqueous solution of 0.01g/L-100g/L, ultrasonic reaction 10-120min, obtain the upper conversion nano granule that Hyperbranched Polymer with Terminal Amido is modified, with the centrifugal 20min of the rotating speed of 8000 turns/min, repeatedly wash with distilled water and ethanol, and dry at 60oC.
(4) the upper conversion nano Granular composite modified by the 10-50mg Hyperbranched Polymer with Terminal Amido obtained in step 3 is in 10ml deionized water, add folic acid FA, 100mg sodium hydroxide of 150-300mg, ultrasonic reaction a period of time, centrifugation, repeatedly wash with distilled water and ethanol, dry.
Preferably, the mol ratio of the Y:Yb:Er/Tm in described step (1) is 69%-78%:20%-30%:1%-2%.
Preferably, upper conversion nano granule prepared by described step (1) is six side's phases, particle diameter 1-100nm.
Preferably, the ultrasonic time of step (4) is 1-24h.
The synthesis of Hyperbranched Polymer with Terminal Amido is referred to following open source literature: Zhang Feng, Chen Yuyue, Zhang Desuo, Hua Yanrong, Zhao Bing. the preparation of Hyperbranched Polymer with Terminal Amido and quaternary ammonium salt thereof and performance [J]. polymer material science and engineering, 2009,25 (8): 141-144；CN200710020794.8 super-branching reactive dye salt-free dyeing auxiliary；Colorationtechnology, 2007,123 (6): 351-357；AATCCREVIEW, 2010,10 (6): 56-60；BIOMACROMOLECULES, 2010,11 (1): 245-251；CHEMICALRESEARCHINCHINESEUNIVERSITIES, 2005,21 (3): 345-354.
Compared with prior art, it is an advantage of the current invention that:
The present invention replaces the oleic acid of upper conversion nano particle surface initially with Hyperbranched Polymer with Terminal Amido, is prepared for a kind of good water solubility, the upper conversion nano granule that luminous intensity is high.Amine-terminated hyperbranced compound is the dissaving polymer of a kind of structure height branching, superior solubility, has better water solublity than commonly used aminoacid, polymine etc., and more amino-NH is contained on surface2.Then utilization-NH2With-COOH reaction by folacin coupled on upper conversion nano granule.On the folacin coupled water solublity of preparation, conversion nano granule has the advantages such as good dispersion, biocompatibility and targeting, can be used for the targeted imaging of cancer cell.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is expanded on further.
Embodiment 1:
By the Y (CF of 0.78mmol3COO)3, 0.2mmol Yb (CF3COO)3, 0.02mmol Er (CF3COO)310mmol sodium fluoride (NaF) and 20ml organic solvent (10ml oleic acid OA+10ml carbon octadecylene ODE) join in 50mL three-neck flask and are heated to 120 DEG C; it is continually fed into nitrogen protection and heats 1h; then 320 ° of C magnetic agitation 1h it is warmed up to the speed of 1 ° of C/min; naturally cool to room temperature, add dehydrated alcohol, be centrifuged and be precipitated; again repeatedly by water and washing with alcohol, finally give the upper conversion nano granule that may be dissolved in hexamethylene and hexane.
5mL Tetrafluoroboric acid nitrous NOBF by the 5mL up-conversion luminescence nano-particle hexane dispersion soln of 1g/L Yu 0.6g/L4Dichloromethane solution at room temperature mixes, and is shaken gently for by mixture, until upper conversion nano particle precipitation, it is then centrifuged for separating, remove supernatant, be more again scattered in water, 1:10 by volume, add the Hyperbranched Polymer with Terminal Amido aqueous solution of 1g/L, ultrasonic reaction 30min, obtains the upper conversion nano granule that Hyperbranched Polymer with Terminal Amido is modified, centrifugation, repeatedly wash with distilled water and ethanol, and dry at 60oC.
The upper conversion nano Granular composite modified by 10mg Hyperbranched Polymer with Terminal Amido, in 10ml deionized water, adds folic acid FA, 100mg sodium hydroxide of 150mg, ultrasonic reaction 5h, centrifugation, repeatedly washs with distilled water and ethanol, dry.
Embodiment 2:
By the Y (CF of 0.69mmol3COO)3, 0.3mmol Yb (CF3COO)3, 0.01mmol Er (CF3COO)310mmol sodium fluoride (NaF) and 20ml organic solvent (10ml oleic acid OA+10ml carbon octadecylene ODE) join in 50mL three-neck flask and are heated to 120 DEG C; it is continually fed into nitrogen protection and heats 1h; then 320 ° of C magnetic agitation 1h it is warmed up to the speed of 1 ° of C/min; naturally cool to room temperature, add dehydrated alcohol, be centrifuged and be precipitated; again repeatedly by water and washing with alcohol, finally give the upper conversion nano granule that may be dissolved in hexamethylene and hexane.
5mL Tetrafluoroboric acid nitrous NOBF by the 5mL up-conversion luminescence nano-particle hexane dispersion soln of 2g/L Yu 0.3g/L4Dichloromethane solution at room temperature mixes, and is shaken gently for by mixture, until upper conversion nano particle precipitation, it is then centrifuged for separating, remove supernatant, be more again scattered in water, 1:1 by volume, add the Hyperbranched Polymer with Terminal Amido aqueous solution of 5g/L, ultrasonic reaction 60min, obtains the upper conversion nano granule that Hyperbranched Polymer with Terminal Amido is modified, centrifugation, repeatedly wash with distilled water and ethanol, and dry at 60oC.
The upper conversion nano Granular composite modified by 20mg Hyperbranched Polymer with Terminal Amido, in 10ml deionized water, adds folic acid FA, 100mg sodium hydroxide of 200mg, ultrasonic reaction 10h, centrifugation, repeatedly washs with distilled water and ethanol, dry.
Embodiment 3:
By the Y (CF of 0.78mmol3COO)3, 0.2mmol Yb (CF3COO)3, 0.02mmol Tm (CF3COO)310mmol sodium fluoride (NaF) and 20ml organic solvent (10ml oleic acid OA+10ml carbon octadecylene ODE) join in 50mL three-neck flask and are heated to 120 DEG C; it is continually fed into nitrogen protection and heats 1h; then 320 ° of C magnetic agitation 1h it is warmed up to the speed of 1 ° of C/min; naturally cool to room temperature, add dehydrated alcohol, be centrifuged and be precipitated; again repeatedly by water and washing with alcohol, finally give the upper conversion nano granule that may be dissolved in hexamethylene and hexane.
5mL Tetrafluoroboric acid nitrous NOBF by the 5mL up-conversion luminescence nano-particle hexane dispersion soln of 2g/L Yu 0.6g/L4Dichloromethane solution at room temperature mixes, and is shaken gently for by mixture, until upper conversion nano particle precipitation, it is then centrifuged for separating, remove supernatant, be more again scattered in water, 1:10 by volume, add the Hyperbranched Polymer with Terminal Amido aqueous solution of 0.5g/L, ultrasonic reaction 30min, obtains the upper conversion nano granule that Hyperbranched Polymer with Terminal Amido is modified, centrifugation, repeatedly wash with distilled water and ethanol, and dry at 60oC.
The upper conversion nano Granular composite modified by 30mg Hyperbranched Polymer with Terminal Amido, in 10ml deionized water, adds folic acid FA, 100mg sodium hydroxide of 250mg, ultrasonic reaction 12h, centrifugation, repeatedly washs with distilled water and ethanol, dry.
Embodiment 4:
By the Y (CF of 0.69mmol3COO)3, 0.3mmol Yb (CF3COO)3, 0.01mmol Tm (CF3COO)310mmol sodium fluoride (NaF) and 20ml organic solvent (10ml oleic acid OA+10ml carbon octadecylene ODE) join in 50mL three-neck flask and are heated to 120 DEG C; it is continually fed into nitrogen protection and heats 1h; then 320 ° of C magnetic agitation 1h it is warmed up to the speed of 1 ° of C/min; naturally cool to room temperature, add dehydrated alcohol, be centrifuged and be precipitated; again repeatedly by water and washing with alcohol, finally give the upper conversion nano granule that may be dissolved in hexamethylene and hexane.
5mL Tetrafluoroboric acid nitrous NOBF by the 5mL up-conversion luminescence nano-particle hexane dispersion soln of 5g/L Yu 0.1g/L4Dichloromethane solution at room temperature mixes, and is shaken gently for by mixture, until upper conversion nano particle precipitation, it is then centrifuged for separating, remove supernatant, be more again scattered in water, 1:1 by volume, add the Hyperbranched Polymer with Terminal Amido aqueous solution of 20g/L, ultrasonic reaction 90min, obtains the upper conversion nano granule that Hyperbranched Polymer with Terminal Amido is modified, centrifugation, repeatedly wash with distilled water and ethanol, and dry at 60oC.
The upper conversion nano Granular composite modified by 50mg Hyperbranched Polymer with Terminal Amido, in 10ml deionized water, adds folic acid FA, 100mg sodium hydroxide of 300mg, ultrasonic reaction 20h, centrifugation, repeatedly washs with distilled water and ethanol, dry.
Obviously, the above embodiment of the present invention is only for clearly demonstrating example of the present invention, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot all of embodiment be given exhaustive.Every belong to apparent change that technical scheme amplified out or the variation row still in protection scope of the present invention.
Claims (5)
1. the preparation method of conversion nano granule on water solublity one kind folacin coupled, it is characterised in that:
Step one, by the Y (CF that total amount of substance is 1mmol3COO)3、Yb(CF3COO)3、Er(CF3COO)3Or Tm (CF3COO)3, 10mmol sodium fluoride and the mixed organic solvents that is made up of 10mL oleic acid and 10mL carbon octadecylene join in 50mL three-neck flask and be heated to 120 DEG C; it is continually fed into nitrogen protection and heats 1h; then 320 DEG C and magnetic agitation 1h are risen to the heating rate of 1 ° of C/min; naturally cool to room temperature; add dehydrated alcohol; it is centrifuged and is precipitated, more repeatedly by water and washing with alcohol, finally give the upper conversion nano granule that may be dissolved in hexamethylene and hexane；
Step 2, by the 5mL Tetrafluoroboric acid nitrous NOBF of the 5mL up-conversion luminescence nano-particle hexane dispersion soln of 1-5g/L Yu 0.1-0.6g/L4Dichloromethane solution at room temperature mixes, and is shaken gently for by mixture, until upper conversion nano particle precipitation, is then centrifuged for separating, removes supernatant；
Step 3, the up-conversion luminescence nano-particle obtained in step 2 is scattered in water again, 1:1-1:10 by volume, add the dissaving polymer aqueous solution of 0.01g/L-100g/L, ultrasonic reaction 10-120min, obtains the upper conversion nano granule that dissaving polymer is modified, centrifugation, repeatedly wash with distilled water and ethanol, and dry at 60oC；
Step 4, the upper conversion nano Granular composite modified by the 10-50mg dissaving polymer obtained in step 3, in 10ml deionized water, adds folic acid FA, 100mg sodium hydroxide of 150mg, ultrasonic reaction a period of time, centrifugation, repeatedly washs with distilled water and ethanol, dry.
2. the preparation method of conversion nano granule on a kind of folacin coupled water solublity according to claim 1, it is characterised in that the mol ratio of the Y:Yb:Er/Tm described in step one is 69%-78%:20%-30%:1%-2%.
3. the preparation method of conversion nano granule on a kind of folacin coupled water solublity according to claim 1, it is characterised in that the up-conversion luminescence nano-particle of step one preparation is six side's phases, particle diameter 1-100nm.
4. the preparation method of conversion nano granule on a kind of folacin coupled water solublity according to claim 1, it is characterised in that the dissaving polymer described in step 3 is Hyperbranched Polymer with Terminal Amido.
5. the preparation method of conversion nano granule on a kind of folacin coupled water solublity according to claim 1, it is characterised in that the ultrasonic time described in step 4 is 1-24h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410702168.7A CN104371728B (en) | 2014-11-28 | 2014-11-28 | Conversion nano granule and preparation method thereof on a kind of folacin coupled water solublity |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410702168.7A CN104371728B (en) | 2014-11-28 | 2014-11-28 | Conversion nano granule and preparation method thereof on a kind of folacin coupled water solublity |
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| Publication Number | Publication Date |
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| CN104371728A CN104371728A (en) | 2015-02-25 |
| CN104371728B true CN104371728B (en) | 2016-06-29 |
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