CN104194790B - One is conversion nano crystalline substance and preparation and application thereof on superpower multi-photon for super-resolution imaging - Google Patents
One is conversion nano crystalline substance and preparation and application thereof on superpower multi-photon for super-resolution imaging Download PDFInfo
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Abstract
The present invention relates to conversion nano crystalline substance on superpower multi-photon for a kind of super-resolution imaging. A kind of conversion nano crystalline substance on superpower multi-photon for super-resolution imaging, average grain diameter is that the hexagonal crystal of 20～50nm singly disperses tetrafluoro yttrium natrium nanocrystalline mutually, and therein codope rare earth ytterbium ion and thulium ion, mole doping content of ytterbium ion is 10%-49%, and mole doping content of thulium ion is 0.1%-2%. Advantage of the present invention be by forming core/growth separate, rare earth ion species is chosen, prepared by doping content regulate and control method single disperse tetrafluoro yttrium natrium nanocrystalline have size pattern evenly controlled, can produce the characteristic of superpower multi-photon up-conversion luminescence, be applicable to super-resolution imaging.
Description
Technical field
The invention belongs to materials science field, relate in particular to a kind of super-resolution imaging with on superpower multi-photonConversion nano crystalline substance.
Background technology
The spatial resolution of optical microphotograph imaging is subject to the restriction of optical diffraction, i.e. the Abbe limit breaks through the Abbe utmost pointThe novel optical microtechnic of limit is a past important key scientific challenges for many years. Recently, at far field fluorescenceIn imaging, in order to break through this diffraction limit, there are a series of super-resolution new technologies, comprised that high-resolution is photosensitiveLocation microtechnic, random optics are rebuild microtechnic, stimulated emission impairment microtechnic. Wherein, be excitedOne large feature of transmitting impairment microtechnic is that lateral resolution can improve 10 to 15 times than diffraction limit, quiltThink a kind of powerful optical image technology that can realize sub-diffraction resolution. Compare electron microscope etc. itsHis high-resolution microtechnic, stimulated emission impairment microtechnic possesses original position and Real Time Observation sampleSuperiority. But so far, stimulated emission impairment microtechnic is also in the state in a development, many grindingStudying carefully group still actively improves it in vertical many-side. Wherein, the photostability of optical probe and multichannelDurability is a major issue urgently to be resolved hurrily.
Adopt rare earth ion doped upper conversion nano crystalline substance can solve more compactly this as optical probeProblem. Upper conversion nano crystalline substance is widely used in biomedical sector, and research shows, compares organicThis class optical probe of dyestuff, upper conversion nano crystalline substance still has extremely strong light under the strong shooting condition of nanoscaleLearn stability. On the other hand, the fluorescent emission of upper conversion nano crystalline substance is to depend near infrared light to turn to visible rayChange the process of this anti-Stokes transition, therefore can effectively suppress the autofluorescence of biological tissue, therebyGreatly improve signal to noise ratio. Meanwhile, infrared light has larger penetration capacity in vivo than visible ray.
While utilizing conversion nano crystalline substance on multi-photon as the optical probe of super-resolution imaging, the optical resolution of systemRate can be passed through formulaCalculate, wherein λ is incident wavelength, the numerical aperture that NA is microcobjective,N is number of photons. Visible, in the situation that up-conversion fluorescence is enough strong, number of photons is more, and resolution ratio is higher,Imaging effect is better. But under normal circumstances, on multi-photon, the efficiency of switching transition is always well below listPhoton or two photon transition often present the intensity difference distance of the order of magnitude in spectroscopy. For example,, in routineIn spectral detection, the up-conversion luminescence of ytterbium ion and thulium ion codope, its three-photon blue light strength is often1/1000 order of magnitude of two-photon near-infrared intensity, and four photon blue lights are almost difficult to survey especially. Therefore,Develop the nanocrystalline of superpower multi-photon up-conversion luminescence has before very important application in super-resolution imagingScape.
Summary of the invention
The object of this invention is to provide conversion nano crystalline substance and preparation thereof on superpower multi-photon for a kind of super-resolution imagingAnd using method, by the inventive method prepare and use nanocrystallinely can produce conversion on superpower multi-photon and send outLight, is applicable to super-resolution imaging.
Technical scheme of the present invention is:
A kind of conversion nano crystalline substance on superpower multi-photon for super-resolution imaging, six sides that average grain diameter is 20～50nmCrystalline phase list disperses tetrafluoro yttrium natrium nanocrystalline, and therein codope rare earth ytterbium ion and thulium ion, ytterbium ionMole doping content be 10%-49%, mole doping content of thulium ion is 0.1%-2%.
The preparation method of conversion nano crystalline substance on superpower multi-photon, its step is as follows:
(1) rare-earth salts is dissolved in deionized water, forms the solution of 0.2mol/L, then press rare earth ionIt is 90% oleic acid, 1-octadecylene that mole adds purity, at 150 DEG C of uncovered mix and blends, forms lightAfter yellow transparent solution, be cooled to room temperature;
(2) by dissolution of sodium hydroxide in methyl alcohol, form the solution of 1mol/L; Ammonium fluoride is dissolved in methyl alcohol,Form the solution of 0.4mol/L; Two kinds of solution are mixed with 1:4;
(3) be 4:1 by mole total amount of fluorine ion and rare earth ion, get the described mixing of above-mentioned steps (2) moltenLiquid adds in the described mixed solution of above-mentioned steps (1), is uniformly mixed 30 minutes at 50 DEG C; Rise subsequentlyTemperature is to 100 DEG C, after methyl alcohol is volatilized naturally or vacuumizing and drain, under argon gas or nitrogen protection, with 10DEG C/speed of min is warming up to 290～300 DEG C, and mix and blend, after 1～3 hour, is cooled to room temperature;
(4) by acetone or alcohol precipitation, centrifugal for the solution in above-mentioned steps (3), clear with cyclohexane, ethanolWash for several times; The sediment obtaining is dispersed in cyclohexane, forms clear solution.
In technique scheme, described rare-earth salts is acetic acid yttrium, acetic acid ytterbium, acetic acid thulium or yttrium chloride, chlorineChange ytterbium, thulium chloride.
The using method of conversion nano crystalline substance on superpower multi-photon, its step is as follows:
(1) clear solution is diluted to the solution of 0.1～1mmol/L with cyclohexane, is spin-coated on the glass that 0.17mm is thickOn glass sheet, form monodisperse particles layer;
(2) adopt 980nm Laser Focusing to excite single tetrafluoro yttrium natrium nanocrystalline that disperses, produce conversion on multiband and send outLight;
(3) by upper transfer power intensity rule I ∝ Pn, I is fluorescence intensity, and P is exciting power, and n is number of photons,Regulate exciting power to two-photon, three-photon radiation transistion saturation threshold, produce on four superpower photonsConversion blue-light-emitting.
The present invention compared with prior art, has following beneficial features: by forming core/growth separate, rare earth fromIt is equal that single dispersion tetrafluoro yttrium natrium nanocrystalline that subcategory is chosen, prepared by doping content regulate and control method has size patternEven controlled, can produce the characteristic of superpower multi-photon up-conversion luminescence, be applicable to super-resolution imaging; The present inventionThe upper conversion nano crystalline substance of preparation, compared with existing dye class optical probe, has photostability, inanimate object tissueAutofluorescence, strong penetration capacity; The saturated conversion nano crystalline substance that excites that the present invention uses excites with existing routineUpper conversion nano crystalline phase ratio, there is superpower multi-photon up-conversion luminescence, be highly suitable for super-resolution imaging.
Detailed description of the invention
Below by embodiment, the invention will be further described, and specific embodiment is as follows.
Embodiment 1
A kind of conversion nano crystalline substance on superpower multi-photon for super-resolution imaging, size pattern is controlled hexagonal crystal evenlySingly mutually disperse tetrafluoro yttrium natrium nanocrystalline, and therein codope rare earth ytterbium ion and thulium ion.
The method of conversion nano crystalline substance on superpower multi-photon, measures the acetic acid yttrium aqueous solution 1.6ml of 0.2mol/L,The acetic acid ytterbium aqueous solution 0.36ml of 0.2mol/L, the acetic acid thulium aqueous solution 0.04ml of 0.2mol/L, purity90% oleic acid 3ml, 1-octadecylene 7ml, was placed in there-necked flask, 150 DEG C of uncovered agitating heating 30 minutes;Be cooled to after room temperature, add the methyl alcohol mixed solution 4.3ml of NaOH and ammonium fluoride, be warming up to 50 DEG C and openMouth agitating heating 30 minutes; Be warming up to 100 DEG C, after methyl alcohol volatilization, pass into argon gas, continue to be warming up to 290DEG C, be incubated cooling after 90 minutes; With acetone precipitation, centrifugal, with cyclohexane, ethanol cleaning 2 times; To obtainSediment be dispersed in 4ml cyclohexane, form clear solution, obtain upper conversion nano crystalline substance of the present invention.
Above-mentioned nanocrystalline through the detection of X-ray electronic diffraction, be six good side's phase tetrafluoro yttrium sodium of crystallinity, warpTransmission electron microscope observing is the average grain diameter spherical monodisperse nano-particle particle that is 22nm. Clear solution is rare with cyclohexaneRelease the solution to 0.1～1mmol/L, be spin-coated on the sheet glass that 0.17mm is thick, form monodisperse particles layer.Adopt 980nm Laser Focusing number of shots single tetrafluoro yttrium natrium nanocrystalline that disperses, produce multiband up-conversion luminescence;By upper transfer power intensity rule I ∝ Pn, I is fluorescence intensity, and P is exciting power, and n is number of photons, regulates and swashsSend out power density to 106W/cm2Magnitude, produce on four superpower photons and change blue-light-emitting, i.e. 448nm placeFluorescence intensity is 72 times of 800nm place.
Embodiment 2
A kind of conversion nano crystalline substance on superpower multi-photon for super-resolution imaging, size pattern is controlled hexagonal crystal evenlySingly mutually disperse tetrafluoro yttrium natrium nanocrystalline, and therein codope rare earth ytterbium ion and thulium ion.
The method of conversion nano crystalline substance on superpower multi-photon, measures the acetic acid yttrium aqueous solution 1ml of 0.2mol/L, 0.2The acetic acid ytterbium aqueous solution 0.98ml of mol/L, the acetic acid thulium aqueous solution 0.02ml of 0.2mol/L, purity 90%Oleic acid 3ml, 1-octadecylene 7ml, was placed in there-necked flask, 150 DEG C of uncovered agitating heating 30 minutes; CoolingTo room temperature, add the methyl alcohol mixed solution 4.3ml of NaOH and ammonium fluoride, be warming up to 50 DEG C of uncovered stirringMix heating 30 minutes; Be warming up to 100 DEG C, after methyl alcohol volatilization, pass into argon gas, continue to be warming up to 290 DEG C,Be incubated cooling after 90 minutes; With acetone precipitation, centrifugal, with cyclohexane, ethanol cleaning 2 times; Heavy by what obtainShallow lake thing is dispersed in 4ml cyclohexane, forms clear solution, obtains upper conversion nano crystalline substance of the present invention.
Above-mentioned nanocrystalline through the detection of X-ray electronic diffraction, be six good side's phase tetrafluoro yttrium sodium of crystallinity, warpTransmission electron microscope observing is the average grain diameter spherical monodisperse nano-particle particle that is 25nm. Clear solution is rare with cyclohexaneRelease the solution to 0.1～1mmol/L, be spin-coated on the sheet glass that 0.17mm is thick, form monodisperse particles layer.Adopt 980nm Laser Focusing number of shots single tetrafluoro yttrium natrium nanocrystalline that disperses, produce multiband up-conversion luminescence;Regulate exciting power density to 106W/cm2Magnitude, produces on four superpower photons and changes blue-light-emitting, be i.e. 448nmThe fluorescence intensity at place is 78 times of 800nm place.
Embodiment 3
A kind of conversion nano crystalline substance on superpower multi-photon for super-resolution imaging, size pattern is controlled hexagonal crystal evenlySingly mutually disperse tetrafluoro yttrium natrium nanocrystalline, and therein codope rare earth ytterbium ion and thulium ion.
The method of conversion nano crystalline substance on superpower multi-photon, measures the acetic acid yttrium aqueous solution 1.6ml of 0.2mol/L,The acetic acid ytterbium aqueous solution 0.36ml of 0.2mol/L, the acetic acid thulium aqueous solution 0.04ml of 0.2mol/L, purity90% oleic acid 7ml, 1-octadecylene 7ml, was placed in there-necked flask, 150 DEG C of uncovered agitating heating 30 minutes;Be cooled to after room temperature, add the methyl alcohol mixed solution 4.3ml of NaOH and ammonium fluoride, be warming up to 50 DEG C and openMouth agitating heating 30 minutes; Be warming up to 100 DEG C, after methyl alcohol volatilization, pass into argon gas, continue to be warming up to 290DEG C, be incubated cooling after 90 minutes; With acetone precipitation, centrifugal, with cyclohexane, ethanol cleaning 2 times; To obtainSediment be dispersed in 4ml cyclohexane, form clear solution, obtain upper conversion nano crystalline substance of the present invention.
Above-mentioned nanocrystalline through the detection of X-ray electronic diffraction, be six good side's phase tetrafluoro yttrium sodium of crystallinity, warpTransmission electron microscope observing, for average length is 45nm, the bar-shaped monodisperse particles that mean breadth is 25nm. WillClear solution is diluted to the solution of 0.1～1mmol/L with cyclohexane, is spin-coated on the sheet glass that 0.17mm is thick,Form monodisperse particles layer. Adopt 980nm Laser Focusing number of shots single tetrafluoro yttrium natrium nanocrystalline that disperses, produceRaw multiband up-conversion luminescence; Regulate exciting power density to 105W/cm2Magnitude, produces on four superpower photonsConversion blue-light-emitting, the fluorescence intensity at 448nm place is 110 times of 800nm place.
Claims (1)
1. a preparation method for conversion nano crystalline substance on superpower multi-photon for super-resolution imaging, described conversion nano crystalline substance is that average grain diameter isThe size pattern of 20～50nm evenly controlled hexagonal crystal singly disperses tetrafluoro yttrium natrium nanocrystalline mutually, and therein codope rare earthYtterbium ion and thulium ion, mole doping content of ytterbium ion is 10%-49%, mole doping content of thulium ion is 0.1%-2%,It is characterized in that, preparation process is as follows:
(1) rare-earth salts is dissolved in deionized water, forms the solution of 0.2mol/L, then add by the mole of rare earth ionPurity is 90% oleic acid, 1-octadecylene, at 150 DEG C of uncovered mix and blends, after formation light yellow transparent solution, is cooled to chamberTemperature;
(2) by dissolution of sodium hydroxide in methyl alcohol, form the solution of 1mol/L; Ammonium fluoride is dissolved in methyl alcohol, forms 0.4The solution of mol/L; Two kinds of solution are mixed with 1:4;
(3) be 4:1 by mole total amount of fluorine ion and rare earth ion, get the described mixed solution of above-mentioned steps (2) and add above-mentionedIn mixed solution described in step (1), be uniformly mixed 30 minutes at 50 DEG C; Be warming up to subsequently 100 DEG C, by methyl alcohol natureVolatilization or vacuumize and drain after, under argon gas or nitrogen protection, be warming up to 290～300 DEG C with the speed of 10 DEG C/min, mixedClose and stir after 1～3 hour, be cooled to room temperature;
(4) by acetone or alcohol precipitation, centrifugal for the solution in above-mentioned steps (3), with cyclohexane, ethanol cleaning several; WillThe sediment obtaining is dispersed in cyclohexane, forms clear solution;
Described rare-earth salts is acetic acid yttrium, acetic acid ytterbium, acetic acid thulium or yttrium chloride, ytterbium chloride, thulium chloride.
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