CN104910915A - Preparation method and application of hydrophilic rare earth nano-material - Google Patents
Preparation method and application of hydrophilic rare earth nano-material Download PDFInfo
- Publication number
- CN104910915A CN104910915A CN201510200772.4A CN201510200772A CN104910915A CN 104910915 A CN104910915 A CN 104910915A CN 201510200772 A CN201510200772 A CN 201510200772A CN 104910915 A CN104910915 A CN 104910915A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- nano material
- preparation
- wetting ability
- earth nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 49
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 39
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 rare earth nitrate Chemical class 0.000 claims abstract description 13
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 4
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 4
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 3
- 239000011780 sodium chloride Substances 0.000 claims abstract description 3
- 238000009736 wetting Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 9
- 238000003384 imaging method Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000010335 hydrothermal treatment Methods 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- 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 claims description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- 231100000252 nontoxic Toxicity 0.000 claims description 4
- 230000003000 nontoxic effect Effects 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229940001516 sodium nitrate Drugs 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- HASUJDLTAYUWCO-UHFFFAOYSA-N 2-aminoundecanoic acid Chemical compound CCCCCCCCCC(N)C(O)=O HASUJDLTAYUWCO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 150000008542 L-histidines Chemical class 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 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 description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052773 Promethium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical group [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- 229960000304 folic acid Drugs 0.000 claims description 2
- 235000019152 folic acid Nutrition 0.000 claims description 2
- 239000011724 folic acid Substances 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 2
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 150000003016 phosphoric acids Chemical class 0.000 claims 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- 238000012984 biological imaging Methods 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 239000011775 sodium fluoride Substances 0.000 abstract 1
- 235000013024 sodium fluoride Nutrition 0.000 abstract 1
- 238000006557 surface reaction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000090 biomarker Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 208000019065 cervical carcinoma Diseases 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000013399 early diagnosis Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004232 linoleic acid Drugs 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 1
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
The present invention belongs to the technical field of nano-materials, and particularly relates to a preparation method and application of a hydrophilic rare earth nano-material, and the method is as follows: a rare earth nitrate and chloride as rare earth sources, sodium fluoride and ammonia fluoride as fluoride sources, sodium chloride and sodium nitrate as sodium sources, ethylene glycol and ethanol as solvents and a surface functionalization ligand are mixed and stirred evenly according to certain mole ratio, the evenly-stirred solution is transferred into a hydrothermal kettle for water/solvent heat treatment. After natural cooling, deionized water and ethanol are used for in turn centrifuging, and the obtained precipitate is put into an oven for baking for 6-12 h at 60-120 DEG C under the condition of air to obtain the hydrophilic rare earth nano-material, by use of the one-step water/solvent heat method, the preparation technology is simple, the obtained hydrophilic rare earth nano-material has good stability, high luminous efficiency, adjustable size, controllable morphology, short cycle, low cost, high yield, no toxicity, and no pollution, and can be widely used in security, biological molecular fluorescent tag, biological imaging and other fields.
Description
Technical field
The present invention relates to a kind of wetting ability rare earth nano material, and provide the preparation method of this material, belong to technical field of nano material.
Background technology
Rare earth element shows the characteristics such as the long and Stocke displacement of excellent monochromaticity, anti-light Bleachability, fluorescence lifetime is large and has a wide range of applications in fields such as materials because of the electronic structure of its uniqueness.In Study of Nanoscale Rare Earth Luminescent Materials, rear-earth-doped upper conversion nano luminescent material, because it can absorb comparatively energy photons and send higher-energy photon, make it in bio-imaging, biomarker and biological detection, have stronger superiority, as little in toxicity, chemical stability is high, good light stability, absorption and many advantages such as emission band is narrow, the life-span is long.Near-infrared laser also brings many advantages as its excitaton source in addition, as darker light penetration depth, to biological tissue almost not damaged, without background fluorescence, signal to noise ratio is high, sensitivity is high.And after its link targeted molecular, can marked tumor biological cells and tissues specifically, for realizing early diagnosis of tumor and treatment provides new method.But, Study of Nanoscale Rare Earth Luminescent Materials for biomarker, biological detection and bio-imaging must meet following 4 requirements: 1) water-soluble, and requires that its surface has active group (as-COOH ,-NH2 ,-SH etc.) and is convenient to they and biomolecular reaction; 2) wetting ability, wetting ability is conducive to rare earth nano material and is scattered in water; 3) small size, and morphology controllable; 4) luminous efficiency is high.
The method preparing the Study of Nanoscale Rare Earth Luminescent Materials of morphology controllable at present mainly contains water/solvent-thermal method, high temperature thermal decomposition method, coprecipitation method etc., but the surface ligand of Study of Nanoscale Rare Earth Luminescent Materials prepared by these methods is (as oleic acid, linolic acid) be generally hydrophobic, namely water is insoluble in, in order to realize its application at biological field, Study of Nanoscale Rare Earth Luminescent Materials need obtain water-soluble by further surface modification.The surface modifying method developed at present has: polymer encapsulation, surperficial silated method and surface ligand oxidation style etc., but these method preparation process are complicated and the permanent stability of prepared material are bad, the more difficult control of pattern, cost is high, even can affect the optical property of nanoparticle.
In sum, although utilize surface modifying method also can prepare water miscible Study of Nanoscale Rare Earth Luminescent Materials, its complicated process of preparation, cost is high, and the more difficult control of pattern, even can affect the optical property of nanoparticle.And involved in the present invention be a kind of preparation method and application thereof of the easy hydrophilic rare earth nano material of a step Hydrothermal Synthesis.Hydrophilic rare earth nano material not only good stability prepared by present method, technique is simple, and luminous efficiency is high, and size is little, morphology controllable, and the cycle is short, and cost is low, and reaction yield is high, and use range is extensive.
Recent study more and the water miscible Study of Nanoscale Rare Earth Luminescent Materials with practical value mainly contains following several: is the water miscible Study of Nanoscale Rare Earth Luminescent Materials prepared by hot coprecipitation method involved by patent CN 101914328 A.Water miscible nano luminescent material described in this patent needs the time of protection of inert gas longer in actual experiment process, and whole experimental implementation flow process is too loaded down with trivial details, is not suitable for industrial large-scale mass production.
Is the amphipathic rare earth nano material using microemulsion Hydrothermal Synthesis involved by patent CN101289217 A.Amphipathic nano material described in this patent has used the pharmaceutical chemicals that toluene and acetone etc. are poisonous to human body in actual experiment process, thus has limitation in actual applications.
Is rare earth nano material with a kind of Supramolecular self assembly of solvent-thermal process involved by patent CN101851001 A.The rare earth nano material of the Supramolecular self assembly described in this patent needs to dewater in actual experiment process, and whole experimental implementation flow process is too loaded down with trivial details, is not suitable for industrial large-scale mass production.
Summary of the invention
The object of this invention is to provide a kind of preparation method and application thereof of hydrophilic rare earth nano material, the method synthesis technique is simple, and the cycle is short, does not need special equipment, and it is nontoxic to test pharmaceutical chemicals used, environmental protection.The wetting ability rare earth nano material infrared up conversion efficiency obtained is high, thermostability and chemical stability good, the little and luminous intensity advantages of higher of size, can be widely used in the fields such as biomarker, biological detection and bio-imaging.
Its concrete steps of preparation method that the invention provides above-mentioned hydrophilic rare earth nano material are:
(1) be 0.8 ~ 16 in molar ratio by anion ligand and rare earth compound, the mol ratio of sodium salt and rare earth ion is 0.1 ~ 10, be dissolved in certain ethanol or ethylene glycol, and at 20 DEG C ~ 60 DEG C vigorous stirring 15 ~ 30min, then surface-functionalized part salt is joined in the solution of above-mentioned vigorous stirring, and the mol ratio of surface-functionalized part and rare earth ion is 0.1 ~ 30, and transfer in 25 or 50mL water heating kettle after continuing to stir 20min ~ 1h, carry out hydrothermal treatment consists.After naturally cooling, with deionized water and ethanol centrifugal 2 ~ 5 times successively (time centrifugal, rotating speed is 6000 ~ 10000r/min), again obtained precipitation to be put in baking oven under air conditions 60 DEG C ~ 120 DEG C and to dry 6 ~ 12h, obtain required wetting ability rare earth nano material.
(2) described in the above-mentioned methods rare earth compound is the one or more combination in lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), the nitrate of yttrium (Y) or muriate; Anion ligand is Sodium Fluoride (NaF) or ammonium fluoride (NH4F), and sodium salt is sodium-chlor (NaCl) or SODIUMNITRATE (NaNO
3); Surface-functionalized part is the one or more combination wherein such as hexanodioic acid, nonane diacid, pentanedioic acid, folic acid, polyoxyethylene glycol two carboxylic acid, aminoundecanoic acid, 6-aminocaprolc acid, the acid of 8-naphthalene acid anhydride, L-Histidines.
(3) described in the above-mentioned methods hydrothermal treatment consists temperature is 160 DEG C ~ 180 DEG C.
(4) described in the above-mentioned methods hydrothermal conditions is 15min ~ 8h.
Wetting ability rare earth nano material preparation method described is in the above-mentioned methods one step hydro thermal method, preparation technology is simple, and obtain wetting ability rare earth nano material good stability, luminous efficiency is high, size adjustable, morphology controllable, the cycle is short, and cost is low, productive rate is high, nontoxic, pollution-free, can be widely used in false proof, the field such as biomolecules fluorescent mark, bio-imaging.
Beneficial effect of the present invention is:
The present invention adopts one step hydro thermal method synthetic method, simple to operate, and experimental period is short, can obtain pollution-free, good stability, luminous efficiency is high, size adjustable, morphology controllable, cost is low, and productive rate is high, nontoxic, can be widely used in false proof, the field such as biomolecules fluorescent mark, bio-imaging.Compared with its water-solubility rare-earth nano luminescent material, its experiment is easy and simple to handle, and the test period is short, and raw material sources enriches, and can be mass, business use value is high.
Accompanying drawing explanation
Fig. 1 is α-NaYF prepared by embodiment of the present invention 1-3
4: Yb/Er up-conversion fluorescence utilizing emitted light spectrogram (980nm excites)
Fig. 2 is β-NaYF prepared by embodiment of the present invention 4-6
4: Yb/Er up-conversion fluorescence utilizing emitted light spectrogram (980nm excites)
Fig. 3 is β-NaYF prepared by the embodiment of the present invention 7
4: the bio-imaging figure of Yb/Er on human cervical carcinoma cell.
Embodiment
Embodiment 1: under room temperature, by SODIUMNITRATE, ammonium fluoride, Yttrium trinitrate, ytterbium nitrate, Erbium trinitrate, be be dissolved in 20mL ethanol at 2: 40: 0.39: 0.1: 0.01 in molar ratio, and at 20 DEG C ~ 60 DEG C vigorous stirring 20 ~ 30min, then the surface-functionalized part hexanodioic acid of 6mmol is joined in the solution of above-mentioned vigorous stirring, and transfer in 25mL water heating kettle after continuing to stir 30min, under 180 DEG C of loft drier, carry out hydrothermal treatment consists 2h.After naturally cooling, with deionized water and ethanol centrifugal 3 times successively (time centrifugal, rotating speed is 8000r/min), then obtained precipitation to be put in baking oven under air conditions 60 DEG C and to dry 10h, obtain required wetting ability rare earth nano material.
Embodiment 2: by the preparation method of embodiment 1 by prepared wetting ability β-NaYF
4: Yb/Er nano material with mark human cervical carcinoma cell and bio-imaging.
The above, be only present pre-ferred embodiments, therefore can not limit scope of the present invention according to this, and the equivalence namely done according to the scope of the claims of the present invention and description changes and modifies, and all should still belong to scope of the present invention.
Claims (5)
1. the preparation method of a wetting ability rare earth nano material, it is characterized by concrete steps as follows: be 0.8 ~ 16 in molar ratio by anion ligand and rare earth compound, the mol ratio of sodium salt and rare earth ion is 0.1 ~ 10, be dissolved in certain ethanol or ethylene glycol, and at 20 DEG C ~ 60 DEG C vigorous stirring 15 ~ 30min, then surface-functionalized part salt is joined in the solution of above-mentioned vigorous stirring, and the mol ratio of surface-functionalized part and rare earth ion is 0.1 ~ 30, and transfer in 25 or 50mL water heating kettle after continuing to stir 20min ~ 1h, carry out hydrothermal treatment consists.After naturally cooling, with deionized water and ethanol centrifugal 2 ~ 5 times successively (time centrifugal, rotating speed is 6000 ~ 10000r/min), again obtained precipitation to be put in baking oven under air conditions 60 DEG C ~ 120 DEG C and to dry 6 ~ 12h, obtain required wetting ability rare earth nano material.
2. prepare wetting ability rare earth nano material as claimed in claim 1 for one kind, it is characterized in that: described rare earth compound is lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pn), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), all salt of yttrium (Y), include but not limited to nitrate, vitriol, phosphoric acid salt, one or more combination in organic acid salt and muriate, anion ligand is fluorion, and source includes but not limited to Sodium Fluoride (NaF), ammonium fluoride (NH
4f) or organic fluorine source, sodium salt is sodium-chlor (NaCl) or SODIUMNITRATE (NaNO
3), surface-functionalized part is the one or more combination wherein such as hexanodioic acid, nonane diacid, pentanedioic acid, folic acid, polyoxyethylene glycol two carboxylic acid, aminoundecanoic acid, 6-aminocaprolc acid, the acid of 8-naphthalene acid anhydride, L-Histidines.
3. a preparation wetting ability rare earth nano material as claimed in claim 1, is characterized in that: described hydrothermal treatment consists temperature is 160 DEG C ~ 180 DEG C.
4. a preparation wetting ability rare earth nano material as claimed in claim 1, is characterized in that: described hydrothermal conditions is 15min ~ 8h.
5. the preparation wetting ability rare earth nano material as described in as arbitrary in Claims 1 to 4, is characterized in that: described wetting ability rare earth nano material preparation method is a step water/solvent-thermal method, and preparation technology is simple, obtain wetting ability rare earth nano material good stability, luminous efficiency is high, size adjustable, morphology controllable, cycle is short, cost is low, and productive rate is high, nontoxic, pollution-free, can be widely used in false proof, the field such as biomolecules fluorescent mark, bio-imaging.6. the preparation wetting ability rare earth nano material as described in as arbitrary in Claims 1 to 4, is characterized in that: reaction solvent used in described wetting ability rare earth nano material preparation method is: water, ethanol, ethylene glycol, polyoxyethylene glycol etc. and composition thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510200772.4A CN104910915A (en) | 2015-04-22 | 2015-04-22 | Preparation method and application of hydrophilic rare earth nano-material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510200772.4A CN104910915A (en) | 2015-04-22 | 2015-04-22 | Preparation method and application of hydrophilic rare earth nano-material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104910915A true CN104910915A (en) | 2015-09-16 |
Family
ID=54080369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510200772.4A Pending CN104910915A (en) | 2015-04-22 | 2015-04-22 | Preparation method and application of hydrophilic rare earth nano-material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104910915A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733586A (en) * | 2016-04-27 | 2016-07-06 | 武汉理工大学 | Method for preparing AREF4:Ln<3+> up-conversion microcrystals by combining thermal decomposition method with hydrothermal method |
| CN106854169A (en) * | 2016-12-30 | 2017-06-16 | 山东大学 | A kind of amino-acid rare earth coordinates high-efficiency fluorescence powder and preparation method thereof |
| CN109231883A (en) * | 2018-09-19 | 2019-01-18 | 蚌埠星烁新材料科技有限公司 | A kind of weather-resistant and high-strength degree lacquer |
| CN109319821A (en) * | 2018-10-31 | 2019-02-12 | 南京科技职业学院 | A kind of preparation method of hydrophily rare earth nano material |
| CN111732952A (en) * | 2020-06-10 | 2020-10-02 | 浙江理工大学 | Preparation method of water-soluble and surface-functionalized rare earth nano material |
| CN114574207A (en) * | 2022-03-14 | 2022-06-03 | 甘肃省科学院传感技术研究所 | Red light emitting rare earth ion doped up-conversion nano material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914382A (en) * | 2010-06-24 | 2010-12-15 | 复旦大学 | Method for preparing water-soluble and surface-functionalized rare earth nanometer material |
| CN102703081A (en) * | 2012-05-25 | 2012-10-03 | 吉林大学 | Water-soluble rare earth doped gadolinium sodium tetrafluoride fluorescent marked nano-crystal, and preparation method thereof |
| CN103087705A (en) * | 2013-01-16 | 2013-05-08 | 大连理工大学 | High-strength rare earth-doped up-conversion luminescence nanometer material and preparation method thereof |
| CN103112882A (en) * | 2013-03-08 | 2013-05-22 | 南开大学 | Preparation method of targeting near-infrared NaYF4 up-conversion nanocrystal |
| CN103275721A (en) * | 2013-06-14 | 2013-09-04 | 北京化工大学 | Monodisperse sodium yttrium tetrafluoride luminescent nano-particle coated with chitosan derivative and preparation method thereof |
| CN103436263A (en) * | 2013-09-09 | 2013-12-11 | 天津师范大学 | Preparation method of water-soluble red-green light tunable rare-earth doped up-conversion nano-material |
-
2015
- 2015-04-22 CN CN201510200772.4A patent/CN104910915A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914382A (en) * | 2010-06-24 | 2010-12-15 | 复旦大学 | Method for preparing water-soluble and surface-functionalized rare earth nanometer material |
| CN102703081A (en) * | 2012-05-25 | 2012-10-03 | 吉林大学 | Water-soluble rare earth doped gadolinium sodium tetrafluoride fluorescent marked nano-crystal, and preparation method thereof |
| CN103087705A (en) * | 2013-01-16 | 2013-05-08 | 大连理工大学 | High-strength rare earth-doped up-conversion luminescence nanometer material and preparation method thereof |
| CN103112882A (en) * | 2013-03-08 | 2013-05-22 | 南开大学 | Preparation method of targeting near-infrared NaYF4 up-conversion nanocrystal |
| CN103275721A (en) * | 2013-06-14 | 2013-09-04 | 北京化工大学 | Monodisperse sodium yttrium tetrafluoride luminescent nano-particle coated with chitosan derivative and preparation method thereof |
| CN103436263A (en) * | 2013-09-09 | 2013-12-11 | 天津师范大学 | Preparation method of water-soluble red-green light tunable rare-earth doped up-conversion nano-material |
Non-Patent Citations (1)
| Title |
|---|
| 陈志钢等: "水溶性NaYF_4∶Yb,Er纳米颗粒的溶剂热合成及其上转换发光性能", 《材料导报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733586A (en) * | 2016-04-27 | 2016-07-06 | 武汉理工大学 | Method for preparing AREF4:Ln<3+> up-conversion microcrystals by combining thermal decomposition method with hydrothermal method |
| CN105733586B (en) * | 2016-04-27 | 2018-09-11 | 武汉理工大学 | A kind of thermal decomposition-hydro-thermal combination preparation AREF4:Ln3+The preparation method of upper conversion micron crystalline substance |
| CN106854169A (en) * | 2016-12-30 | 2017-06-16 | 山东大学 | A kind of amino-acid rare earth coordinates high-efficiency fluorescence powder and preparation method thereof |
| CN106854169B (en) * | 2016-12-30 | 2018-10-09 | 山东大学 | A kind of amino acid-rare earth cooperation high-efficiency fluorescence powder and preparation method thereof |
| CN109231883A (en) * | 2018-09-19 | 2019-01-18 | 蚌埠星烁新材料科技有限公司 | A kind of weather-resistant and high-strength degree lacquer |
| CN109319821A (en) * | 2018-10-31 | 2019-02-12 | 南京科技职业学院 | A kind of preparation method of hydrophily rare earth nano material |
| CN111732952A (en) * | 2020-06-10 | 2020-10-02 | 浙江理工大学 | Preparation method of water-soluble and surface-functionalized rare earth nano material |
| CN111732952B (en) * | 2020-06-10 | 2023-02-17 | 浙江理工大学 | Preparation method of water-soluble and surface-functionalized rare earth nano material |
| CN114574207A (en) * | 2022-03-14 | 2022-06-03 | 甘肃省科学院传感技术研究所 | Red light emitting rare earth ion doped up-conversion nano material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104910915A (en) | Preparation method and application of hydrophilic rare earth nano-material | |
| CN104017581B (en) | Photothermal deformation nano material and preparations and applicatio method thereof | |
| CN105694888B (en) | A kind of Mg2+Adulterate NaREF4Upconverting fluorescent material and preparation method thereof | |
| CN102268259A (en) | Luminescent centre regionally doped rare earth upconversion luminescent material and preparation method thereof | |
| CN110878207A (en) | Up-conversion nanometer optical switch material and preparation method thereof | |
| CN113817469B (en) | Ultra-bright monochromatic up-conversion nano probe for excitation/emission in biological window and preparation method and application thereof | |
| CN103215037A (en) | Method for synthesizing upconversion fluorescence hollow nanosphere based on sodium polyacrylate microsphere template synthesis | |
| CN103436263B (en) | Preparation method of water-soluble red-green light tunable rare-earth doped up-conversion nano-material | |
| CN101787278A (en) | Pyrolytic synthesis method for water-soluble fluorescent carbon nano-particles | |
| CN103540318B (en) | Preparation method of rare earth complex grafted luminescent titanium dioxide mesoporous microsphere | |
| CN105670628A (en) | Up-conversion fluorescent powder with greatly improved red light and excellent monochromaticity and method for preparing up-conversion fluorescent powder | |
| CN101787284B (en) | Upconversion luminescent hollow sphere using yttrium fluoride as ground substance and preparation method thereof | |
| CN107529514B (en) | Preparation method and application of fluorine ion-doped carbon dots | |
| CN102504821A (en) | Preparation method of rare earth-doped sodium gadolinium tetrafluoride nanomaterial | |
| CN103351859B (en) | Method for preparing Ag/Y2O3:Yb<3+>/Er<3+> composite nanotubes with up-conversion light emitting function | |
| CN103289701A (en) | Method for preparing heterogeneous nuclear shell structure CaF2:20Yb, 2Ho@NaXF4 nanocrystalline | |
| CN105462589A (en) | Core-shell structured Fe3O4@GdVO4:Eu<3+> magnetic nanometer luminescent material and preparation method thereof | |
| CN105061403A (en) | Multifunctional group pyridazinone compounds, application of multifunctional group pyridazinone compounds serving as orange organic light-emitting material and preparation method of multifunctional group pyridazinone compounds | |
| CN101787283B (en) | Preparation method of hollow luminous ball assembled by Eu-doped yttrium fluoride nano rods | |
| CN105778902A (en) | Preparation method of rare earth hollow nanocrystal | |
| CN102344807A (en) | Solvothermal synthesis method for NaLn(MoO4)2 micron crystal | |
| CN105238391A (en) | Preparation method for multiple light sources vanadium-based mesoporous organic and inorganic hybrid luminescent material | |
| CN113403072A (en) | Rare earth doped hafnium lithium fluoride based up-conversion luminescent nano material with pore structure and preparation method thereof | |
| CN105385447A (en) | Low-cost method for preparing NaREF4 type upconversion light-emitting porous microspheres in large quantities | |
| CN110003278A (en) | A kind of six core tripolyphosphazene europium complex luminescent materials of excited by visible light and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150916 |
|
| WD01 | Invention patent application deemed withdrawn after publication |