CN103756668A - Core-shell type rare earth up-conversion composite nanoparticle and preparation method thereof - Google Patents
Core-shell type rare earth up-conversion composite nanoparticle and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a core-shell type rare earth up-conversion composite nanoparticle and a preparation method thereof. The silver ion coated with silicon dioxide nanoparticle is the core of the composite nanoparticle; the core is externally coated with a rare earth oxide to form a nanoparticle with a core shell structure and the particle size of 80-90nm, and the chemical formula is Ag@SiO2@Lu2O3:Gd/Yb/Er; the particle size of the silver core is 18-22nm; the thickness of the silicon dioxide shell is 17-33nm; the thickness of the rare earth oxide shell layer is 3.5-4.5nm. The fluorescence intensity of the composite nanoparticle provided by the invention is enhanced by 30 times. The nanoparticle is applied to HeLa cell imaging, and relatively strong fluorescence can be detected. The invention relates to the first metal-enhanced fluorescence study taking Lu2O3:Gd, Yb, Er as an up-conversion fluorophore, and the 30 times metal-enhanced fluorescence value is also the strongest in the existing up-conversion nanocrystal. With the enhancement effect, the prepared composite nanoparticles become a fluorescence nano probe with great application prospect, and can be widely applied to the fields of high-sensitivity biological, medical and optical detection.
Description
Technical field
The present invention relates to a kind of upper conversion composite nanoparticle and preparation method thereof, particularly on a kind of core-shell rare-earth, change composite nanoparticle and preparation method thereof.
Background technology
Along with the fast development of nanosecond science and technology, rare earth up-conversion luminescence nanometer crystal receives many concerns because of its unique optics and chemical property.With respect to other fluorescent materials (as organic dye or quantum dot), rare earth upconversion nano crystal (UCNs) presents many advantages, hypotoxicity for example, high chemical stability, narrowband emission, larger anti-stoke shift, darker light penetration depth and spatial resolution, to biological tissue's not damaged etc.; In addition, rare earth up-conversion luminescence only needs the near infrared continuous laser device (typical excitation wavelength is 980nm) of low power density.But UCNs is conventionally because cause up-conversion luminescence efficiency low in structural defect, little absorption cross section has also caused its launching efficiency to be restricted simultaneously.So UCNs is applied to high sensitive medical science and biological detection is still subject to certain limitation, as single molecule assays, lively imaging and other optical application.In order to strengthen up-conversion fluorescence intensity and to expand the application of UCNs, worked out at present certain methods, for example wrap up silica shell, manufacture nucleocapsid structure, Gd
3+ion doping, introduces noble metal nano particles etc.As everyone knows, introducing noble metal nano particles is a kind of strategy of effective enhancing fluorescence intensity for metal-enhanced fluorescence (MEF).MEF results from the interaction of fluorophore and metal nanoparticle (silver and gold) plasma resonance, cause metallic nano-particle local Electromagnetic enhancement around, thereby enhancing launching efficiency, make the radiative decay speed of fluorophore also strengthen, this two aspect is the fluorescence intensity of acting in conjunction enhancing fluorophore all simultaneously thereupon.MEF is at organic dye, and the application of quantum dot and rare earth compounding is extensively studied, and this has wherein also comprised the work of doing before us.But, up to now till MEF be applied to UCNs and also rarely have report.The more important thing is, in existing report, its intensification factor is not ideal enough.The NaYF reporting recently
4: Yb, Er@SiO
2@Ag and Ag@SiO
2@Y
2o
3: it is 4 times and 14.4 times that the maximum metal of Er core-shell nano structure strengthens fluorescence, and wherein 14.4 is the maximum value in the document of having reported.But these enhancings may still be difficult to meet the requirement that high sensitive detects.Therefore, further research is to obtain higher reinforced effects, and the up-conversion nanoparticles that obtains larger fluorescence intensity seems and is extremely necessary.
Summary of the invention
One of object of the present invention is to provide on a kind of core-shell rare-earth changes composite nanoparticle.
Two of object of the present invention is to provide the preparation method of this composite nanoparticle.
For achieving the above object, the present invention adopts following technical scheme:
On a kind of core-shell rare-earth, change composite nanoparticle, it is characterized in that this composite nanoparticle be the be coated with silicon oxide silver ions of nano particle be core, this core is coated with rare earth oxide and forms the nanoparticle that particle diameter is the nucleocapsid structure of 80～90nm, and its chemical formula is: Ag@SiO
2@Lu
2o
3: Gd/Yb/Er; The particle diameter of wherein said galactic nucleus is: 18～22nm; The thickness of silica shell is: 17～33nm; Rare earth oxide shell thickness is: 3.5～4.5 nm.
Above-mentioned rare earth oxide is lutecium oxide, ytterbium oxide, gadolinium sesquioxide or Erbium trioxide.
Prepare a method of changing composite nanoparticle on above-mentioned core-shell rare-earth, it is characterized in that the concrete steps of the method are:
A. Silver Nitrate and polyvinylpyrrolidone are dissolved in ethylene glycol by the mol ratio of 9:1 ~ 10:1, wherein the concentration of Silver Nitrate is 0.03 ~ 0.04mol/L, speed with 10 ℃/min is heated to 120 ℃ again, and be incubated 1h, cooling, in solution, add acetone, separate out precipitation, centrifugation, makes nanometer silver and is dissolved in the aqueous solution that is made into 10mg/mL in deionized water;
B. polyoxy is dissolved in deionized water by 27:52:1 ~ 30:55:1 mass ratio for nanometer silver in ethene (5) nonylplenyl ether, hexanaphthene, step a gained nano-silver water solution, stir and after 20 minutes, add catalyst levels, again stir 25 minutes, the mixed solution that adds tetraethoxy and hexanaphthene to be mixed with by the volume ratio of 1:1, the mol ratio of wherein said nanometer silver and TEOS is 6:1 ~ 7:1, after stirring 48h, add acetone, separate out precipitation, centrifugation, wash with water again after alcohol wash, obtain the silver of coated with silica, i.e. Ag@SiO
2;
C. rare earth oxide is dissolved in to concentrated hydrochloric acid and water by the mixed solution of the volume ratio of 3:1, is warming up to 90 ℃, react to solution change clear, continue heating, solvent evaporated, rare earth chloride is with white powder crystallization; Then by step b gained Ag@SiO
2, gained rare earth chloride and urea is added to the water by the mass ratio of 1:5:44, magnetic agitation, after 20 minutes, is heated to 90 ℃, and maintains 2 h, cooling rear centrifugation, alcohol wash, dry, then high-temperature calcination 3h at 700 ℃, obtains products A g@SiO
2@Lu
2o
3: Gd/Yb/Er nanoparticle.
Core-shell composite nanoparticle Ag@SiO of the present invention
2@Lu
2o
3: Gd/Yb/Er, and its performance is studied.Research is found, due to MEF and Lu
2o
3: the new type structure of hud that Gd/Yb/Er forms, with the simple SiO without metal nano silver
2@Lu
2o
3: Gd/Yb/Er nanoparticle is compared, and novel composite nanoparticle fluorescence intensity has strengthened 30 times.This nanoparticle is applied to HeLa cell imaging, stronger fluorescence can be detected.This is for the first time with Lu
2o
3: Gd, Yb, the metal-enhanced fluorescence research that Er carries out as up-conversion fluorescence group, the metal-enhanced fluorescence value of 30 times is also the strongest in existing upper conversion nano crystalline substance.This increase effect makes prepared composite nanoparticle become a kind of fluorescent nano probe that has very much application prospect, can be widely used in high-sensitive biology, medical science and optical detection field.
Accompanying drawing explanation
Fig. 1 is preparation method's of the present invention schema.
Fig. 2 is SiO
2@Lu
2o
3: Gd/Yb/Er (A) and Ag@SiO
2@Lu
2o
3: Gd/Yb/Er (B) XRF diffraction (XRD) spectrogram.
Fig. 3 is Ag@SiO
2(A) and Ag@SiO
2@Lu
2o
3: Gd/Yb/Er (B) transmission electron microscope (TEM) photo, Ag (A is inner) and Lu
2o
3(B is inner) is high resolution projection (HRTEM) photo.
Fig. 4 is Ag@SiO
2@Lu
2o
3: Gd/Yb/Er is energy dispersion type XRF (EDX) collection of illustrative plates.
Fig. 5 Ag@SiO
2, SiO
2@Lu
2o
3: Gd/Yb/Er and Ag@SiO
2@Lu
2o
3: Gd/Yb/Er ultraviolet-visible absorption spectroscopy.
Fig. 6 SiO
2@Lu
2o
3: Gd/Yb/Er(A) with Ag@SiO
2@Lu
2o
3: the fluorescence emission spectrum of Gd/Yb/Er (B).
Fig. 7 light field liver cancer cell cell (A), green glow image (520-560 nm) (B), ruddiness image (625-700 nm) channeis (C), B and C stacking diagram (D), A and D stacking diagram (E).
Fig. 8 up-conversion fluorescence signal scanning figure, and region, extracellular (1 and 5, tenuigenin region (2 and 4), nuclear area (3).
Fig. 9 is three-dimensional liver cancer cell fluorescence imaging figure.
Embodiment
experimental raw:lutecium oxide, ytterbium oxide, gadolinium sesquioxide, Erbium trioxide (purity: 99.999%, Yaolong Non-ferrous Metal Co. Ltd., Shanghai), polyoxy is for ethene (5) nonylplenyl ether (CO-520), polyvinylpyrrolidone (Sigma-aldrich), concentrated hydrochloric acid, Silver Nitrate, ethylene glycol, tetraethoxy, polyvinylpyrrolidone, urea, ammoniacal liquor (traditional Chinese medicines reagent)
Embodiment mono-: referring to Fig. 1, concrete steps are:
1. the preparation of Ag nanometer ball:0.4gAgNO3 solid and 10 g PVP are dissolved in 75ml ethylene glycol, mixture are heated to 120 ° of C with the speed of 10 ° of C/min, and are incubated 1h, cooling, in solution, add a large amount of acetone, separate out precipitation, centrifugation, is placed in dehydrated alcohol and preserves, in order to using.
2 core-shell particle preparation:4ml CO-520,10 ml hexanaphthenes, 2 ml water, 0.15g nanometer silver adds in 30ml round-bottomed flask, stirs after 20 minutes and adds 50 μ L ammoniacal liquor, again stirs 25 minutes, add 100 TEOS mixed solutions (50% TEOS/50% hexanaphthene), after stirring 48h, add proper amount of acetone, centrifugation, washing alcohol wash is preserved in order to using for several times.
.Ag@SiO 2 @Lu 2 o 3 : the preparation of Gd/Yb/Er nucleocapsid structure composite nanoparticle:first respectively by rare earth oxide Lu
2o
3, Gd
2o
3, Yb
2o
3, Er
2o
3be dissolved in appropriate concentrated nitric acid and water, through unnecessary acid and the water of evaporative removal, crystallization makes rare earth chloride.Then by 0.05 g Ag@SiO
2, 2.2g urea, 0.75 mmol LnCl
3(Ln=54%Lu, 24%Gd, 20%Yb, 2%Er) join in 200 mL water after mixing, magnetic agitation is after 20 minutes, being placed in Erlenmeyer flask is heated to 90 ° of C and maintains 2 h, cooling rear centrifugation, alcohol wash 3 times, is dried 12h by the product making in 80 ° of C, then high-temperature calcination 3h under 700 ° of C, obtains products A g@SiO
2@Lu
2o
3: Gd/Yb/Er nanoparticle.
laser Scanning Confocal Microscope imaging
HeLa cell is seeded in the Tissue Culture Dish that bottom thickness is 0.17mm, and the cell culture incubator that is placed in 37 ° of C, 5% carbonic acid gas is cultivated after 24h, discards former substratum, adds 200 μ g/mL Ag@SiO
2@Lu
2o
3: Gd/Yb/Er solution, continue to cultivate after 3h, discard nutrient solution, PBS damping fluid for culture dish (pH7.4) cleans cell and removes the Ag@SiO into cell for 3 times
2@Lu
2o
3: Gd/Yb/Er nanoparticle, finally adds 1mL PBS damping fluid.Finally with the confocal laser scanning microscope, CLSM observation of cell imaging that configures 980nm wavelength continuous wave laser.
result and discussion
Referring to Fig. 2.The obvious diffraction peak that has occurred Ag and Lu2O3 in spectrogram A and B.Diffraction peak position in collection of illustrative plates (211,222,400,440,622) matches with the XRD spectral line of standard cube phase Lu2O3 (JCPDS 12-0728).Ag@SiO
2@Lu
2o
3: Gd/Yb/Er occurs that four obvious diffraction peaks (111,200,220 311) are consistent with the XRD standard card of cubic Ag (JCPDS 87-0720), and occurs without the diffraction peak of other impurity.
For observing its pattern of sample and size, sample has been carried out to the mensuration of TEM and HRTEM, as shown in Figure 3.From Fig. 3 A, Ag core globulate, size distribution, in 20nm left and right, is wrapped up SiO
2rear particle is still spherical, and size is even, Ag@SiO
2particle diameter is at 80nm left and right, SiO
2thickness is about 30nm.Fig. 3 B is Ag@SiO
2@Lu
2o
3: the TEM figure of Gd/Yb/Er, nanoparticle forming shape homogeneous spherical, particle diameter is at 88nm left and right, Lu
2o
3: Gd/Yb/Er thickness of the shell is about 4nm.In Fig. 3 A, the upper right corner is the high resolution TEM figure of Ag nanoparticle, can see spacing be 0.241nm corresponding to (111) spacing, this is cube to nanometer Ag.Fig. 3 B upper right corner is Lu
2o
3the high resolution TEM figure of layer, its spacing of lattice be 0.319nm corresponding to (222) spacing, Lu is described
2o
3layer is Emission in Cubic crystal formation.Fig. 4 is Ag@SiO
2@Lu
2o
3: Gd/Yb/Er is EDX collection of illustrative plates, as can be seen from Figure its elementary composition be Ag, Si, O, Lu, Gd, Yb, further proves Ag@SiO
2@Lu
2o
3: Gd/Yb/Er is successfully synthetic.
ultraviolet-visible absorption spectroscopy (UV-Vis) is analyzed
Sample UV-Vis spectrogram as shown in Figure 5, Ag@SiO
2the plasma resonance absorption peak that occurs Ag at 450 nm annexes.Simple Ag nanoparticle plasma resonance absorption peak is near 390nm, parcel SiO
2after, Ag nano particle local specific refractory power is around increased, thereby caused the red shift of Ag particle surface plasma resonance absorption peak.Ag@SiO
2@Lu
2o
3: the plasma resonance absorption peak of Gd/Yb/Er composite particles is positioned at 550nm, relatively Ag@SiO
2have again larger red shift, this is because Ag@SiO
2by Lu
2o
3: Gd/Yb/Er is coated to be formed after nucleocapsid structure, makes Ag@SiO
2the surface refractive index of particle continues to increase, and red shift occurs again in this variation.Ag@SiO
2@Lu
2o
3: in the UV-Vis absorption spectrum of Gd/Yb/Er nanoparticle, there is the surface plasma body resonant vibration absorption peak of Ag, show that Ag core is successfully wrapped in nanoparticle.
fluorescent spectroscopy
SiO
2@Lu
2o
3: Gd/Yb/Er and Ag@SiO
2@Lu
2o
3: Gd/Yb/Er nanoparticle concentration be fluorescence emission spectrum under 1.0 mg/mL as shown in Figure 6, excitation wavelength is 980nm, all shows Er
3+characteristic red light emission peak, the strongest emission peak is positioned at 662nm, corresponding to Er
3+'s
4f
9/2→
4i
15/2transition of electron.At 520nm and 550nm place, there is Er simultaneously
3+'s
2h
11/2→
4i
15/2and
4s
3/2→
4i
15/2characteristic emission transition peak, this is Er
3+feature green emission, but intensity a little less than.
In Fig. 6, Ag@SiO
2@Lu
2o
3: the fluorescence intensity of Gd/Yb/Er composite nanoparticle is compared to does not have silver-colored nanoparticle SiO
2@Lu
2o
3: Gd/Yb/Er exceeds 30 times, and the fluorescence intensity of utilizing the metal-enhanced fluorescence effect of metal nano Ag effectively to improve nanoparticle is described.Its enhanced mechanism may be interpreted as: metallic nano-particle can greatly strengthen metallic nano-particle electromagnetic field around by resonance coupling strong between surface plasmons and photon, and then near the launching efficiency of the twinkler of raising metallic nano-particle, strengthen its radiative decay speed simultaneously.Both coefficient results strengthen the fluorescence intensity of twinkler.In our research, the surface ion resonance body absorption band of silver nanoparticle does not have with the activation wavelength (980nm) of fluorophore overlapping.Can infer thus, increase launching efficiency and do not play a major role in the fluorescence enhancing of prepared composite nanoparticle, what play a crucial role is the radiative decay speed enhancing of system.Certainly, in composite nanoparticle, the separation distance between Ag nanoparticle and fluorophore, the particle diameter of Ag nanoparticle etc. also plays an important role in metal-enhanced fluorescence effect.Reference report, we choose silica shell thickness and galactic nucleus particle diameter is respectively 30nm and 20nm in this research.Result shows, prepared nanoparticle selects the silicon thickness of the shell of this size and galactic nucleus particle diameter can reach desirable fluorescence reinforced effects.
cell imaging
For checking nanocomposite applications is in the possibility of bio-imaging, with 980nm excitation wavelength, HeLa cell is carried out to cell imaging.PBS buffered soln containing 200 μ g/mL nanoparticles is added in HeLa cell, and under 37 oC, incubation is 3 hours, by Laser Scanning Confocal Microscope, observes.As shown in Figure 7, at tenuigenin regional observation, arrived the high light signal at 625-700nm (redness) and 520-560nm (green).In addition, do not enter nucleus in order to verify nano composite material to enter tenuigenin, we have also carried out the quantitative analysis of up-conversion luminescence (UCL) strength of signal, and test is chosen 5 position differences in cell and analyzed respectively its UCL.As seen from Figure 7, there is very high fluorescent signal (region 2 and region 4 are counted as 4000) in HeLa tenuigenin region, and nucleus place does not detect fluorescent signal.
In addition, also carried out the three-dimensional imaging of viable cell, as shown in Figure 8, result further proves that this nanoparticle can enter cell and can be used for cell imaging to result, and nanoparticle is distributed in tenuigenin region after entering cell.
Claims (3)
1. on a core-shell rare-earth, change composite nanoparticle, it is characterized in that this composite nanoparticle be the be coated with silicon oxide silver ions of nano particle be core, this core is coated with rare earth oxide and forms the nanoparticle that particle diameter is the nucleocapsid structure of 80～90nm, and its chemical formula is: Ag@SiO
2@Lu
2o
3: Gd/Yb/Er; The particle diameter of wherein said galactic nucleus is: 18～22nm; The thickness of silica shell is: 17～33nm; Rare earth oxide shell thickness is: 3.5～4.5 nm.
2. on core-shell rare-earth according to claim 1, change composite nanoparticle, it is characterized in that described rare earth oxide is lutecium oxide, ytterbium oxide, gadolinium sesquioxide or Erbium trioxide.
3. prepare a method of changing composite nanoparticle on core-shell rare-earth according to claim 1 and 2, it is characterized in that the concrete steps of the method are:
A. Silver Nitrate and polyvinylpyrrolidone are dissolved in ethylene glycol by the mol ratio of 9:1 ~ 10:1, wherein the concentration of Silver Nitrate is 0.03 ~ 0.04mol/L, speed with 10 ℃/min is heated to 120 ℃ again, and be incubated 1h, cooling, in solution, add acetone, separate out precipitation, centrifugation, makes nanometer silver and is dissolved in the aqueous solution that is made into 10mg/mL in deionized water;
B. polyoxy is dissolved in deionized water by 27:52:1 ~ 30:55:1 mass ratio for nanometer silver in ethene (5) nonylplenyl ether, hexanaphthene, step a gained nano-silver water solution, stir and after 20 minutes, add catalyst levels, again stir 25 minutes, the mixed solution that adds tetraethoxy and hexanaphthene to be mixed with by the volume ratio of 1:1, the mol ratio of wherein said nanometer silver and TEOS is 6:1 ~ 7:1, after stirring 48h, add acetone, separate out precipitation, centrifugation, wash with water again after alcohol wash, obtain the silver of coated with silica, i.e. Ag@SiO
2;
C. rare earth oxide is dissolved in to concentrated hydrochloric acid and water by the mixed solution of the volume ratio of 3:1, is warming up to 90 ℃, react to solution change clear, continue heating, solvent evaporated, rare earth chloride is with white powder crystallization; Then by step b gained Ag@SiO
2, gained rare earth chloride and urea is added to the water by the mass ratio of 1:5:44, magnetic agitation, after 20 minutes, is heated to 90 ℃, and maintains 2 h, cooling rear centrifugation, alcohol wash, dry, then high-temperature calcination 3h at 700 ℃, obtains products A g@SiO
2@Lu
2o
3: Gd/Yb/Er nanoparticle.
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