CN116731717A - Near-infrared squaraine dye sensitized rare earth up-conversion luminescence nano probe, preparation method and application thereof - Google Patents
Near-infrared squaraine dye sensitized rare earth up-conversion luminescence nano probe, preparation method and application thereof Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 93
- IHXWECHPYNPJRR-UHFFFAOYSA-N 3-hydroxycyclobut-2-en-1-one Chemical compound OC1=CC(=O)C1 IHXWECHPYNPJRR-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 44
- 238000004020 luminiscence type Methods 0.000 title claims abstract description 38
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 35
- 239000000523 sample Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 63
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- 150000002500 ions Chemical class 0.000 claims abstract description 11
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 claims abstract description 10
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 13
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 13
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 13
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
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- 239000000203 mixture Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- -1 rare earth chloride Chemical class 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- QDHFHIQKOVNCNC-UHFFFAOYSA-M butane-1-sulfonate Chemical compound CCCCS([O-])(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-M 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
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- 229910017855 NH 4 F Inorganic materials 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 3
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- 239000000975 dye Substances 0.000 abstract description 57
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- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
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- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000729 poly(L-lysine) polymer Polymers 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
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- 150000003248 quinolines Chemical class 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
- C09K11/7773—Halogenides with alkali or alkaline earth metal
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/007—Squaraine dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
Abstract
The invention discloses a near infrared squaric acid dye sensitized rare earth up-conversion luminescence nano probe, a preparation method and application thereof; the probe consists of near infrared squaraine dye and core-shell structure up-conversion nano particles, and the squaraine dye is coordinated to the nano particles through direct ligand exchange to realize up-conversion luminescence enhancement. The preparation method is simple, and the squaraine dye can be coordinated to the rare earth nano particles, wherein the near infrared squaraine dye has an absorption wavelength of 600-900nm and an emission wavelength of 650-950nm, and has better spectrum overlapping with the absorption of sensitizer ions in the core-shell structure up-conversion nano particles, so that the up-conversion luminescence brightness is effectively enhanced under the excitation of near infrared light; compared with the traditional cyanine dye, the squaraine dye sensitized up-conversion nanoparticle has excellent light stability and anti-aggregation induced quenching capability.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a near infrared squaric acid dye sensitized rare earth up-conversion luminescent nano probe, a preparation method and application thereof.
Background
Lanthanide doped up-conversion nanoparticles (UCNPs) are an important class of optical materials, and lanthanide-based up-conversion luminescence (UCL) can be applied in a variety of fields such as bioimaging, multicolor displays, super-resolution nano-microscopy, and photovoltaics. In biological environments, up-conversion imaging can eliminate interference of autofluorescence and allow background-free detection. These advantages make UCNPs a single molecule imaging probe with application prospects, however, the lower brightness of individual nanoparticles limits their application in biological imaging, especially for UCNPs smaller than 20nm.
The near infrared organic dye is introduced into the existing research as a sensitizer to optimize the luminous performance of UCNPs, and is applied to the related fields of photodynamic therapy, optical imaging and the like.
Disclosure of Invention
The invention aims to provide a near-infrared dye sensitized rare earth up-conversion nano probe with high brightness and high light stability, a preparation method and application thereof; the invention coordinates squaraine dye to nano particles through direct ligand exchange to realize up-conversion luminescence enhancement. The preparation method is simple, and the squaraine dye can be coordinated to the rare earth nano particles, wherein the near infrared squaraine dye absorption wavelength has better spectrum overlap with the absorption of sensitizer ions in the core-shell structure up-conversion nano particles, and the up-conversion luminescence brightness can be effectively enhanced under the excitation of near infrared light, so that the method can be used for single-particle imaging.
The technical scheme of the invention is as follows.
The invention provides a near infrared squaraine dye sensitized rare earth up-conversion luminescence nano probe, which consists of near infrared squaraine dye and core-shell structure up-conversion nano particles, wherein the near infrared squaraine dye is coordinated to the core-shell structure up-conversion nano particles through direct ligand exchange to realize up-conversion luminescence enhancement; wherein, the structural formula of the near infrared squaraine dye is as follows:
the core-shell structure up-conversion nano-particle adopts NaYb with high single particle brightness 0.92 Er 0.08 F 4 The structure is used as a core, and the general formula is as follows: naYb 0.92 Er 0.08 F 4 @NaLu 1-x Yb x F 4 @NaLu 1-y-z Nd y Yb z F 4 Wherein x=0.1 to 0.5, y=0.1 to 0.3, and z=0.1 to 0.5.
In the near infrared squaraine dye, squaraine has a stable resonance zwitterionic structure, and an electron donor-acceptor-donor (D-A-D) structure is formed by a four-membered ring with electron deficiency in the center and electron donating groups on two sides. The quinoline derivative is used as an electron donor, so that the molecule has a larger conjugated structure and electron donating capability, can red shift the emission and absorption wavelength to near infrared, and has good light stability, chemical stability and water solubility.
The near infrared squaraine dye has an absorption wavelength of 600-900nm and an emission wavelength of 650-950nm.
In the invention, the preparation method of the near infrared squaric acid dye comprises the following steps:
(1) Dissolving quinaldine and 1, 4-Ding Huangtong in toluene under inert atmosphere, refluxing and stirring, filtering and washing after the reaction is finished, and obtaining a purple solid which is 4- (2-methylquinoline-1-acyl) butane-1-sulfonate; wherein: the mol ratio of quinaldine to 1, 4-Ding Huangtong is 0.95:1-1: 0.95;
(2) Dissolving 4- (2-methylquinoline-1-acyl) butane-1-sulfonate in a mixed solvent consisting of anhydrous toluene and n-butanol, adding squaric acid, refluxing and stirring by a water knockout drum, removing the solvent by rotary evaporation after the reaction is finished to obtain a crude product, and purifying by a column chromatography to obtain a target product; wherein the molar ratio of the 4- (2-methylquinoline-1-acyl) butane-1-sulfonate to the squaric acid is 2:0.95-2:1.05.
In the invention, er is doped in the core of the core-shell structure up-conversion nano particle 3+ Ion by Er 3+ Ions as emitters, doped in the outermost layerNd 3+ As squaraine dye energy acceptor, the intermediate layer is Yb 3+ Doped energy transfer layer, spatially separating Er 3+ And Nd 3+ Ion, prevent Er 3+ And Nd 3+ Deleterious cross-relaxation between ions.
In the invention, the particle diameter of the conversion nano particles on the core-shell structure is less than 20nm, and the structural formula is NaYb 0.92 Er 0.08 F 4 @NaLu 0.9 Yb 0.1 F 4 @NaLu 0.6 Nd 0.3 Yb 0.1 F 4 。
In the invention, the core-shell structure up-conversion nano particles are synthesized by a layer-by-layer epitaxial growth method, and the specific steps are as follows: will contain YbCl 3 And ErCl 3 Adding an aqueous solution of rare earth chloride into a flask containing oleic acid and 1-octadecene, stirring under an inert atmosphere, heating to 155-165 ℃, and evaporating for 30-50min to remove water; cooling to 110-120 deg.c, adding NH fast 4 F and sodium oleate are dissolved for 20-40min and then vacuumized; heating to 285-295 ℃ under the protection of inert atmosphere, maintaining for 40-60min, cooling to room temperature, adding alcohol solvent into a reaction system, separating out precipitate, centrifugally washing to obtain nuclear nano particles, dispersing into cyclohexane and preserving;
(II) to contain LuCl 3 And YbCl 3 Adding an aqueous solution of rare earth chloride into a flask filled with oleic acid and 1-octadecene, stirring under an inert atmosphere, heating to 155-165 ℃, and evaporating for 30-50min in an open manner to remove water to obtain a shell precursor solution; adding the nuclear nanoparticle cyclohexane dispersion liquid obtained in the step (one), and dissolving NH 4 F, stirring a methanol solution of NaOH and F under the protection of inertia, heating at 110-120 ℃ for 20-40min, and removing a low-boiling point solvent and part of water; heating to 285-295 ℃ under the protection of inert atmosphere, keeping the reaction for 20-40min, cooling to room temperature, adding an alcohol solvent into a reaction system, separating out precipitate, centrifugally washing to obtain core-shell nano particles, dispersing the core-shell nano particles into cyclohexane, and preserving;
(III) collecting the extract containing LuCl 3 、NdCl 3 And YbCl 3 Adding aqueous solution of rare earth chloride to the containerStirring the mixture in a flask of oleic acid and 1-octadecene under inert atmosphere, heating to 155-165 ℃, and cooling to room temperature after open evaporation for 30-50min to remove water to obtain a shell precursor solution; adding the core-shell nanoparticle cyclohexane dispersion liquid obtained in the step (II) and dissolving NH 4 F, stirring a methanol solution of NaOH and F under the protection of inert atmosphere, heating at 110-120 ℃ for 20-40min, and removing a low-boiling point solvent and part of water; heating to 285-295 ℃ under the protection of inert atmosphere, keeping the reaction for 30-50min, and then cooling to room temperature; adding an alcohol solvent into the reaction system, precipitating a precipitate, centrifugally washing to obtain the core-shell nano particles of the target product, and dispersing the core-shell nano particles into cyclohexane for storage.
In the invention, near infrared squaraine dye is coordinated to core-shell structure up-conversion nano particles through a direct ligand exchange process in an organic solvent environment; wherein the organic solvent is one or more of chloroform, oleic acid, cyclohexane, n-hexane, toluene or dichloromethane.
The invention also provides a preparation method of the near infrared squaraine dye sensitized rare earth up-conversion luminescence nano probe, which comprises the following steps: and (3) synthesizing a near infrared squaraine dye, namely synthesizing the core-shell structure up-conversion nano-particles, wherein the near infrared squaraine dye is coordinated to the core-shell structure up-conversion nano-particles through direct ligand exchange.
Furthermore, the invention provides application of the near infrared squaraine dye sensitized rare earth up-conversion luminescence nano probe in single particle imaging. When in use, the power density is used: 0.5-10KW/cm 2 The near infrared light source with the laser wavelength of 710-760nm excites and irradiates.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a novel near infrared squaraine dye sensitized rare earth up-conversion luminescence nano probe, which obtains dye sensitized luminescence enhancement by direct ligand exchange coordination of a novel near infrared squaraine dye to the surface of rare earth up-conversion nano particles, and has excitation light source at 730nm and laser power of 30W/cm 2 Under the test condition, the enhancement multiple of the up-conversion luminescence spectrum can reach 50 times;
(2) The near infrared squaraine dye sensitized rare earth up-conversion luminescence nano probe of the invention can be applied to single particle imaging, compared with rare earth up-conversion nano particles (UCNPs), the near infrared squaraine dye sensitized rare earth up-conversion luminescence nano probe uses 2KW/cm 2 The single particle intensity of the UCNPs enhanced by near infrared squaraine dye sensitization is higher than 90 times by the laser excitation of 721 nm;
(3) Compared with the traditional cyanine dye, the squaraine dye sensitized up-conversion nanoparticle organic solvent environment provided by the invention has excellent photostability and anti-aggregation induced quenching capability.
Drawings
Fig. 1 is a working schematic diagram of a near infrared squaraine dye sensitized rare earth up-conversion luminescence nanoprobe in an embodiment of the invention.
FIG. 2 is a molecular structure, absorption spectrum and emission spectrum of the squaraine dye of example 1.
Fig. 3 is a transmission electron micrograph of example 2. Wherein, three sub-graphs are respectively:
and (3) core: naYb 0.92 Er 0.08 F 4 Core-shell: naYb 0.92 Er 0.08 F 4 @NaLu 0.9 Yb 0.1 F 4 And core-shell NaYb 0.92 Er 0.08 F 4 @Na Lu 0.9 Yb 0.1 F 4 @NaLu 0.6 Nd 0.3 Yb 0.1 F 4 A rare earth nanoparticle transmission electron microscope image; the particle sizes were 10, 14 and 18nm, respectively.
FIG. 4 shows SQ-739 sensitized NaYb of example 3 0.92 Er 0.08 F 4 @NaLu 0.9 Yb 0.1 F 4 @NaLu 0.6 Nd 0.3 Yb 0.1 F 4 Up-conversion luminescence enhancement of UCNPs, wherein (a) optimal dye SQ-739 concentration (2.67. Mu.M, lambda ex ＝730nm，30W/cm 2 ) Under the condition of NaYb with or without SQ-739 0.92 Er 0.08 F 4 @NaLu 0.9 Yb 0.1 F 4 @NaLu 0.6 Nd 0.3 Yb 0.1 F 4 Up-conversion emission spectra of UCNPs; (b) The up-conversion luminescence integral intensity of SQ-739 sensitized UCNPs changes curve with dye concentration; (c)Optimal dye SQ-739 concentration (2.67. Mu.M, lambda ex ＝730nm，30W/cm 2 ) Under SQ-739 sensitized NaYb 0.92 Er 0.08 F 4 @NaLu 0.9 Yb 0.1 F 4 @NaLu 0.6 Nd 0.3 Yb 0.1 F 4 The up-conversion luminescence integral intensity of UCNPs varies with the laser irradiation time.
FIG. 5 is a single particle upconversion result for UCNPs enhanced by SQ-739 sensitization of example 4. (a) SQ-739-UCNPs excited at 721nm (2 KW/cm 2 ) Is a representative single particle image of (a). (b) Single particle image of UCNPs without SQ-739. Scale bar: 500nm. (c) Single particle intensity comparison of SQ-739-UCNPs and UCNPs at 721nm excitation.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments accompanied with figures are further described.
Fig. 1 is a working schematic diagram of a near infrared squaraine dye sensitized rare earth up-conversion luminescence nanoprobe in an embodiment of the invention.
Example 1
Synthesis of near-infrared squaraine dye SQ-739
Quinaldine (0.143 g,1 mmol) and 1, 4-Ding Huangtong (0.136 g,1 mmol) were dissolved in anhydrous toluene (25 mL) under Ar and stirred at reflux for 24h. The resulting purple solid was filtered and washed with diethyl ether. To a solution of the resulting 4- (2-methylquinolin-1-yl) butane-1-sulfonate (0.5538 g,2 mmol) in 16mL of anhydrous toluene and 8mL of n-butanol was added squaric acid (0.114 g,1 mmol). After stirring under reflux with a water separator for 12 hours, the solvent was removed by rotary evaporation. The dichloromethane and the methanol are used as eluent, and the column chromatography is adopted to purify the dye to obtain the required near infrared squaric acid dye SQ-739. A DMSO solution of 6.67. Mu.M SQ-739 was prepared, and its absorption spectrum was measured by an ultraviolet-visible absorption spectrometer with a maximum absorption peak at 739nm and its emission spectrum was measured by a fluorescence spectrometer with a maximum emission wavelength at 759nm (FIG. 2). Emission wavelength and design of SQ-739 dyeNd in core-shell rare earth up-conversion nanoparticle outer layer 3+ The absorption of ions has good spectrum overlapping, meets the spectrum overlapping requirement of fluorescence resonance energy transfer, and can be used for dye sensitization up-conversion luminescence.
Example 2
NaYb with particle size of 18nm 0.92 Er 0.08 F 4 @NaLu 0.9 Yb 0.1 F 4 @NaLu 0.6 Nd 0.3 Yb 0.1 F 4 Synthesis of core-shell rare earth up-conversion nano-particles
1mmol (1 mL, 1M) of rare earth chloride aqueous solution (YbCl 3 ：0.92mmol，ErCl 3 :0.08 mmol) was added to a 100mL flask containing 10mL oleic acid and 10mL 1-octadecene. The mixture was stirred under nitrogen, heated to 160 ℃, and evaporated in an open mouth for 1 hour to remove moisture; after cooling to 110-120 ℃, 0.34g of NH is added rapidly 4 F and 2.03g of sodium oleate are dissolved for 30min at 110-120 ℃ and then vacuumized for 30min; heating to 290 ℃ under the protection of nitrogen, maintaining for 50min, and then cooling to room temperature; adding 20mL of ethanol to precipitate nano particles, centrifuging the mixture (15000 rpm,10 min), separating, discarding supernatant, washing the precipitate with a mixture of cyclohexane and ethanol (20 mL, 1:1, v/v), dispersing the nano particles into 10mL of cyclohexane, and preserving;
0.2mmol (0.2 mL, 1M) of rare earth chloride aqueous solution (LuCl) was taken 3 ：0.18mmol，YbCl 3 :0.02 mmol) was added to a 100mL flask containing 3mL oleic acid and 8mL 1-octadecene. Stirring the mixture under nitrogen atmosphere, heating to 160 ℃, and cooling to room temperature after open evaporating for 40min to remove water to obtain a shell precursor solution; adding 2mL of the nuclear nanoparticle cyclohexane dispersion obtained in the previous step and 2.5mL of NH-dissolved solution 4 F (0.75 mmol) and sodium hydroxide (0.5 mmol) under nitrogen protection, heating at 110-120deg.C for 30min, and removing low boiling point solvent and part of water; heating to 290 ℃ under the protection of nitrogen, keeping the reaction for 30min, and then cooling to room temperature; adding 10mL ethanol to precipitate nanoparticles, centrifuging (15000 rpm,10 min) the mixture, removing supernatant, and adding a mixture of cyclohexane and ethanol (10)mL, 1: 1. v/v) washing the precipitate, dispersing the nanoparticles into 10mL of cyclohexane for preservation;
0.2mmol (0.2 mL, 1M) of rare earth chloride aqueous solution (LuCl) was taken 3 ：0.12mmol，NdCl 3 ：0.06mmol，YbCl 3 :0.02 mmol) was added to a 100mL flask containing 3mL oleic acid and 8mL 1-octadecene. Stirring the mixture under nitrogen atmosphere, heating to 160 ℃, and cooling to room temperature after open evaporating for 40min to remove water to obtain a shell precursor solution; 5mL of the core-shell nanoparticle cyclohexane dispersion was added, and 2.5mL of NH was dissolved 4 F (0.75 mmol) and NaOH (0.5 mmol) under nitrogen protection, heating at 110-120deg.C for 30min, and removing low boiling point solvent and part of water; heating to 290 ℃ under the protection of nitrogen, keeping the reaction for 40min, and then cooling to room temperature; adding 10mL of ethanol to precipitate nanoparticles, centrifuging (15000 rpm,10 min) the mixture, removing supernatant, washing precipitate with mixture of cyclohexane and ethanol (10 mL, 1:1, v/v), and dispersing nanoparticles into 10mL of cyclohexane to obtain NaYb with particle diameter of about 18nm (figure 3) 0.92 Er 0.08 F 4 @NaLu 0.9 Yb 0.1 F 4 @NaLu 0.6 Nd 0.3 Yb 0.1 F 4 Core-shell rare earth up-conversion nanoparticles. The obtained core-shell rare earth up-conversion nano-particle has a particle diameter smaller than 20nm, a larger specific surface area can be used for more dye coordination to the surface of the nano-particle, and the outermost layer contains Nd with higher concentration 3+ The distance between dye molecules coordinated with the surface meets the requirement of the distance of fluorescence resonance energy transfer, and high dye sensitization energy transfer efficiency can be realized.
Example 3
SQ-739 sensitized NaYb 0.92 Er 0.08 F 4 @NaLu 0.9 Yb 0.1 F 4 @NaLu 0.6 Nd 0.3 Yb 0.1 F 4 The up-conversion luminescence spectrum of the system varies with the concentration of the added dye SQ-739.
0.5mL of NaYb was taken 0.92 Er 0.08 F 4 @NaLu 0.9 Yb 0.1 F 4 @NaLu 0.6 Nd 0.3 Yb 0.1 F 4 After centrifugation of the cyclohexane dispersion of the core-shell rare earth upconversion nanoparticles, the dispersion was redispersed in 3mL of chloroform to give 157nM chloroform solution of UCNPs. 1.5mL is taken and mixed with 0, 1, 2, 3, 4, 5 and … mu L near infrared squaraine dye solution (0.25 mM SQ-739) respectively in a quartz cuvette, after stirring for 2min, an external laser with the wavelength of 730nm is used as an excitation light source, and the up-conversion luminescence spectrum is tested on an FLS1000 fluorescence spectrometer, wherein the laser power is 30W/cm 2 . Fluorescence spectrograms of the system with the change of dye concentration are obtained respectively. And integrating the spectrum of each spectrogram in the range of 400-700nm to obtain integrated up-conversion luminous intensity corresponding to different dye concentrations, drawing a change curve of the luminous intensity along with the dye concentration by taking the integrated luminous intensity as an ordinate and the dye concentration as an abscissa. (FIG. 4a, FIG. 4 b) at 30W/cm 2 Under the excitation of 730nm laser, when the concentration of SQ-739 is 2.67 mu M, the up-conversion luminescence integral intensity of SQ-739-UCNPs is enhanced by 51 times compared with that of UCNPs, and the up-conversion luminescence intensity is gradually saturated along with the increase of the dye concentration, but after the saturated intensity is reached, the dye is continuously added, the up-conversion luminescence intensity is not obviously reduced, and the near infrared squaric acid dye sensitized rare earth up-conversion nanoparticle system has good anti-aggregation induction quenching capability.
Taking 14 mu L of near infrared squaraine dye solution (0.25 mM SQ-739) and a near infrared squaraine dye sensitized rare earth up-conversion nanoparticle system, and performing a reaction at 730nm (30W/cm 2 ) Under the irradiation of laser, the emission spectrum of 730nm laser is measured every 3 minutes, and the spectrum change condition of 0-36 minutes is monitored. Under the irradiation of 730nm laser for 36min, the luminescence of the near infrared squaraine dye sensitized rare earth up-conversion nanoparticle system is only attenuated by 10%, and the near infrared squaraine dye sensitized rare earth up-conversion nanoparticle system has good luminescence stability.
(FIG. 4 c).
Example 4
NaYb 0.92 Er 0.08 F 4 @NaLu 0.9 Yb 0.1 F 4 @NaLu 0.6 Nd 0.3 Yb 0.1 F 4 And SQ-739 sensitized NaYb 0.92 Er 0.08 F 4 @NaLu 0.9 Yb 0.1 F 4 @NaLu 0.6 Nd 0.3 Yb 0.1 F 4 Is a broad field microscopic single particle imaging of:
dropwise adding 0.5mL of poly-L-lysine aqueous solution (0.1%, w/v) on a clean glass bottom culture dish, incubating for 1 hour, washing excessive poly-L-lysine with deionized water, and adding NaYb 0.92 Er 0.08 F 4 @NaLu 0.9 Yb 0.1 F 4 @NaLu 0.6 Nd 0.3 Yb 0.1 F 4 And SQ-739 sensitized NaYb 0.92 Er 0.08 F 4 @NaLu 0.9 Yb 0.1 F 4 @NaLu 0.6 Nd 0.3 Yb 0.1 F 4 Dispersing the dispersion liquid in oleic acid by ultrasonic, diluting the dispersion liquid in oleic acid by 1000 times, and adding the diluted dispersion liquid into a glass bottom culture dish;
placing the prepared single particle sample on a wide-field microscope stage, exciting with 721nm laser, passing the light emitted by the sample through Nikon100 times objective lens (NA 1.49), passing through 645/75nm bandpass filter, receiving detected signal of up-converted luminescence red light wave band by EMCCD camera, and measuring the wavelength of the light at 2KW/cm for each sample 2 Is to acquire data for about 5 fields of view.
The emission signal of each particle is shown as a point spread function, the point spread function of each particle is fitted with a two-dimensional gaussian function, the luminous intensity of each particle is obtained by dividing the integral of the gaussian fitting function over the full plane by the exposure time and subtracting the background signal, and for each sample, counting the signals of several hundred particles and statistically averaging to obtain the single particle luminous intensity of the sample (fig. 5). At 2KW/cm 2 Under 721nm laser excitation, the single particle up-conversion luminescence intensity of SQ-739-UCNPs is 97 times that of UCNPs without SQ-739, and dye sensitization luminescence enhancement under single particles is obtained.
Claims (9)
1. The near infrared squaraine dye sensitized rare earth up-conversion luminescence nano probe is characterized by comprising near infrared squaraine dye and core-shell structure up-conversion nano particles, wherein the near infrared squaraine dye is coordinated to the core-shell structure up-conversion nano particles through direct ligand exchange to realize up-conversion luminescence enhancement; wherein, the structural formula of the near infrared squaraine dye is as follows:
the core-shell structure up-conversion nano-particle adopts NaYb with high single particle brightness 0.92 Er 0.08 F 4 The structure is used as a core, and the general formula is as follows: naYb 0.92 Er 0.08 F 4 @NaLu 1-x Yb x F 4 @NaLu 1-y-z Nd y Yb z F 4 Wherein x=0.1 to 0.5, y=0.1 to 0.3, and z=0.1 to 0.5.
2. The near infrared squaraine dye-sensitized rare earth up-conversion luminescence nanoprobe according to claim 1, wherein the preparation method of the near infrared squaraine dye is as follows:
(1) Dissolving quinaldine and 1, 4-Ding Huangtong in toluene under inert atmosphere, refluxing and stirring, filtering and washing after the reaction is finished, and obtaining a purple solid which is 4- (2-methylquinoline-1-acyl) butane-1-sulfonate; wherein: the mol ratio of quinaldine to 1, 4-Ding Huangtong is 0.95:1-1: 0.95;
(2) Dissolving 4- (2-methylquinoline-1-acyl) butane-1-sulfonate in a mixed solvent consisting of anhydrous toluene and n-butanol, adding squaric acid, refluxing and stirring by a water knockout drum, removing the solvent by rotary evaporation after the reaction is finished to obtain a crude product, and purifying by a column chromatography to obtain a target product; wherein the molar ratio of the 4- (2-methylquinoline-1-acyl) butane-1-sulfonate to the squaric acid is 2:0.95-2:1.05.
3. The near infrared squaraine dye sensitized rare earth up-conversion luminescence nano probe according to claim 1, wherein the material structural formula of the core-shell structure up-conversion nano particle is NaYb 0.92 Er 0.08 F 4 @NaLu 0.9 Yb 0.1 F 4 @NaLu 0.6 Nd 0.3 Yb 0.1 F 4 The method comprises the steps of carrying out a first treatment on the surface of the Er doping in cores 3+ Ion by Er 3+ Ions are taken as an emitter, and Nd is doped in the outermost layer 3+ As squaraine dye energy acceptor, the intermediate layer is Yb 3+ Doped energy transfer layer, spatially separating Er 3+ And Nd 3+ Ion, prevent Er 3+ And Nd 3+ Deleterious cross-relaxation between ions.
4. The near infrared squaraine dye-sensitized rare earth up-conversion luminescence nanoprobe according to claim 1, wherein the particle size of the core-shell structure up-conversion nanoparticle is less than 20nm.
5. The near infrared squaraine dye-sensitized rare earth up-conversion luminescence nano probe according to claim 1, wherein the core-shell structure up-conversion nano-particles are synthesized by a layer-by-layer epitaxial growth method, and the specific steps are as follows:
will contain YbCl 3 And ErCl 3 Adding an aqueous solution of rare earth chloride into a flask containing oleic acid and 1-octadecene, stirring under an inert atmosphere, heating to 155-165 ℃, and evaporating for 30-50min to remove water; cooling to 110-120 deg.c, adding NH fast 4 F and sodium oleate are dissolved for 20-40min and then vacuumized; heating to 285-295 ℃ under the protection of inert atmosphere, maintaining for 40-60min, cooling to room temperature, adding alcohol solvent into a reaction system, separating out precipitate, centrifugally washing to obtain nuclear nano particles, dispersing into cyclohexane and preserving;
(II) to contain LuCl 3 And YbCl 3 Adding an aqueous solution of rare earth chloride into a flask filled with oleic acid and 1-octadecene, stirring under an inert atmosphere, heating to 155-165 ℃, and evaporating for 30-50min in an open manner to remove water to obtain a shell precursor solution; adding the nuclear nanoparticle cyclohexane dispersion liquid obtained in the step (one), and dissolving NH 4 F, stirring a methanol solution of NaOH and F under the protection of inertia, heating at 110-120 ℃ for 20-40min, and removing a low-boiling point solvent and part of water; heating to 285-295 deg.c under inert atmosphere protection, maintaining reaction for 20-40min, cooling to room temperature, adding alcohol solvent to the reaction system to separate out precipitate, centrifuging and washing to obtain coreShell nanoparticles dispersed in cyclohexane for storage;
(III) collecting the extract containing LuCl 3 、NdCl 3 And YbCl 3 Adding an aqueous solution of rare earth chloride into a flask filled with oleic acid and 1-octadecene, stirring the mixture under an inert atmosphere, heating to 155-165 ℃, and cooling to room temperature after open evaporation for 30-50min to remove water to obtain a shell precursor solution; adding the core-shell nanoparticle cyclohexane dispersion liquid obtained in the step (II) and dissolving NH 4 F, stirring a methanol solution of NaOH and F under the protection of inert atmosphere, heating at 110-120 ℃ for 20-40min, and removing a low-boiling point solvent and part of water; heating to 285-295 ℃ under the protection of inert atmosphere, keeping the reaction for 30-50min, and then cooling to room temperature; adding an alcohol solvent into the reaction system, precipitating a precipitate, centrifugally washing to obtain the core-shell nano particles of the target product, and dispersing the core-shell nano particles into cyclohexane for storage.
6. The near infrared squaraine dye-sensitized rare earth up-conversion luminescent nanoprobe according to claim 1, wherein near infrared squaraine dye is coordinated to core-shell structure up-conversion nanoparticles through a direct ligand exchange process in an organic solvent environment, wherein the organic solvent is one or more of chloroform, oleic acid, cyclohexane, n-hexane, toluene or dichloromethane.
7. A method for preparing a near infrared squaraine dye-sensitized rare earth up-conversion luminescence nanoprobe according to claim 1, which is characterized by comprising the following steps: and (3) synthesizing a near infrared squaraine dye, namely synthesizing the core-shell structure up-conversion nano-particles, wherein the near infrared squaraine dye is coordinated to the core-shell structure up-conversion nano-particles through direct ligand exchange.
8. Use of the near infrared squaraine dye-sensitized rare earth up-conversion luminescence nanoprobe according to claim 1 in single particle imaging.
9. The use according to claim 8, characterized in that in the application a power density is usedDegree: 0.5-10KW/cm 2 The near infrared light source with the laser wavelength of 710-760nm excites and irradiates.
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