CN106085435B - Near-infrared luminous core-shell structure nanometer particle and preparation method thereof - Google Patents

Near-infrared luminous core-shell structure nanometer particle and preparation method thereof Download PDF

Info

Publication number
CN106085435B
CN106085435B CN201610478363.5A CN201610478363A CN106085435B CN 106085435 B CN106085435 B CN 106085435B CN 201610478363 A CN201610478363 A CN 201610478363A CN 106085435 B CN106085435 B CN 106085435B
Authority
CN
China
Prior art keywords
na
nanocrystal
shell structure
core
nd
Prior art date
Application number
CN201610478363.5A
Other languages
Chinese (zh)
Other versions
CN106085435A (en
Inventor
胡慧珊
安保礼
王新
皇亚楠
Original Assignee
上海大学
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 上海大学 filed Critical 上海大学
Priority to CN201610478363.5A priority Critical patent/CN106085435B/en
Publication of CN106085435A publication Critical patent/CN106085435A/en
Application granted granted Critical
Publication of CN106085435B publication Critical patent/CN106085435B/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7772Halogenides
    • C09K11/7773Halogenides with alkali or alkaline earth metal
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02Use of particular materials as binders, particle coatings or suspension media therefor

Abstract

The present invention relates to a kind of near-infrared luminous core-shell structure nanometer particles and preparation method thereof.The core-shell structure nanometer particle is with rare earth compound Na (Y1.5Na0.5)F6:R%Nd is kernel, with NaDyF4Nanocrystal Na (the Y being made of shell1.5Na0.5)F6:r%Nd@NaDyF4, wherein r=5;The nanocrystal has hexagonal phase structure, and the average grain diameter of nanocrystal is 12~15 nm, and wherein the average grain diameter of kernel is 10~13 nm.The grain size of the core-shell structure nanometer particle of the present invention and distribution of shapes is uniform, grain size is small(12~15 nm), good dispersion, toxicity it is smaller.Penetrability in biological tissues is by force, it can be achieved that the live body luminescence imaging of biological tissue.The magnetic resonance imaging of the biological tissue with higher contrast can be obtained simultaneously(MR).With a kind of imaging agents, realizes the imaging of double mode biological living, obtain more biological tissue's information.The stability of the core-shell structure nanometer particle is very good, can be stored 6 months or more in 4 DEG C of refrigerators.

Description

Near-infrared luminous core-shell structure nanometer particle and preparation method thereof

Technical field

Present invention relates particularly to the nuclear shell structure nano grains that near infrared light is sent out under a kind of efficient 808 nm laser excitations Son and preparation method thereof.

Technical background

Since rare earth element ion is by the shielding action of outer layer 5s and 5p track, make rare earth ionfEnergy level is by ligand The influence very little of environment, and there is abundant level structure, so that the emission spectrum of rare earth ion is showed its unique class linear light Spectral property, and the generally variation of the wavelength of emission peak is little.The 4 of rare earth ionfTrack often contains 1 ~ 14 not pairs of electricity Son has stronger paramagnetic performance than the areas d transition metal ions.Therefore rare earth luminous nanoparticle can be used for multi-functional biology Label, to obtain more biological tissue's information.Luminescent nanoparticle is converted under traditional rare earth, mostly with Eu3+、Tb3+、Sm3+、 Dy3+Ion is main sensitization rare earth ion, and excitation emits in ultraviolet-visible area mostly in visual field.Due to ultraviolet and visual field Light cannot generally penetrate inside biological tissue, therefore this kind of rare earth luminescent material cannot be used for the living imaging point of biological tissue Analysis.Ultraviolet light can cause the damage of biomolecule even dead the chronic exposure of biomolecule;It is biological under ultraviolet excitation There are significant self-excitations to fluoresce to cause background interference for tissue.Near-infrared first window(NIR I, 650-900 nm)With The second window of near-infrared(NIR II, 1000-1700 nm)It is certified as " biological transparent window ", NIR II's penetrates depth Degree is up to about 3 cm of biological tissue.Exciting light and transmitting light are respectively positioned on the luminescent marking material in the two sections, biological tissue pair Absorption, scattering and its autofluorescence phenomenon of light etc. will greatly reduce, and the penetration depth of light is deeper, help to realize biological group The living imaging knitted.Therefore, it is higher to be located at the regions NIR I and NIR II, luminous efficiency for design synthesis excitation and transmitting light Rare earth luminous nanoparticle have important practical value.

Invention content

One of the objects of the present invention is to provide a kind of near-infrared luminous core-shell structure nanometer particles.

The second object of the present invention is to provide the preparation method of this core-shell structure nanometer particle.

To achieve the above object, present invention employs following technical solutions:

A kind of near-infrared luminous core-shell structure nanometer particle, it is characterised in that the core-shell structure nanometer particle is with rare earth Compound N a (Y1.5Na0.5)F6:R%Nd is kernel, with NaDyF4Nanocrystal Na (the Y being made of shell1.5Na0.5)F6:r% Nd@NaDyF4, wherein r=5;The nanocrystal has hexagonal phase structure, and the average grain diameter of nanocrystal is 12~15 nm, The average grain diameter of middle kernel is 10~13 nm.

Above-mentioned core-shell nano is the spherical nucleocapsid that average grain diameter is 10~15nm.

A method of preparing above-mentioned near-infrared luminous core-shell structure nanometer particle, it is characterised in that the tool of this method Body step is:

A. the soluble-salt of rare earth ion is dissolved in oleic acid and 1- octadecylenes(The capacity ratio of the two is 6:15)It is formed transparent In clear solution, the methanol mixed solution of sodium hydroxide and ammonium fluoride is added, is added in the soluble-salt of every gram of rare earth ion The ammonium fluoride of the sodium hydroxide of 0.09~0.12 g and 0.135~0.155 g, under stirring, at 250~300 DEG C react 0.5~ 1.5 hours, ethyl alcohol is added and isolates solid product therein again, is dispersed in organic polar solvent after washed, obtains Na (Y1.5Na0.5)F6:R%Nd kernel nanocrystals;

B. sodium trifluoroacetate and soluble dysprosium salt are dissolved in oleic acid with the mixed solution of 1- octadecylenes, step is then added Kernel nanocrystal obtained by rapid a, wherein sodium trifluoroacetate, soluble dysprosium salt rub with the kernel nanocrystal obtained by step a You are than being 1:1:1 to 3:1:1, the methanol solution of ammonium fluoride is added, is reacted 1~3 hour at 260~300 DEG C, ethyl alcohol point is added Solid product is separated out, the nanocrystal Na (Y of the nucleocapsid are obtained after repeatedly washing1.5Na0.5)F6:r%Nd@NaDyF4; The mass ratio of the ammonium fluoride and sodium trifluoroacetate is 1:460.

The characteristics of synthetic method of the present invention is:

1. synthetic method is simple and convenient, easy to operate.

2. equipment is simple, complicated equipment is not needed.

3. the particle diameter distribution of nano-particle is uniform, good dispersion, toxicity is low.

Description of the drawings

Fig. 1 Na (Y1.5Na0.5)F6:Nd nanocrystals and Na (Y1.5Na0.5)F6:Nd@NaDyF4Nanocrystal swashs in 808nm Luminescent spectrum under light excitation.

Fig. 2 Na (Y1.5Na0.5)F6:Nd kernels (2a) and Na (Y1.5Na0.5)F6:Nd@NaDyF4Nucleocapsid (2b's) receives The transmission electron microscope photo of meter Jing Ti.

Fig. 3 Na (Y1.5Na0.5)F6:The XRD diffracting spectrums of Nd nanocrystals.

Fig. 4 Na (Y1.5Na0.5)F6:Nd@NaDyF4The XRD diffracting spectrums of nanocrystal.

Fig. 5 Na (Y1.5Na0.5)F6:Nd@NaDyF4The energy dispersion X-ray figure of nanocrystal.

Specific implementation mode

Embodiment one:Na(Y1.5Na0.5)F6:The preparation method of Nd kernel nanocrystals.

Concretely, 0.95 mmol chloric acid yttrium and 0.05 mmol chloric acid neodymiums are added to 6 mL oleic acid and 15 mL1- ten Under nitrogen protection, clear transparent solutions are formed after 1 hour in 130 DEG C of reactions for the in the mixed solvent of eight alkene composition.Delay again after cooling It is slow to be added containing the 10 mL methanol solutions that quality is 0.09 g sodium hydroxides and 0.135 g ammonium fluorides, it is sufficiently stirred, nitrogen is protected Under shield, 270 DEG C the reaction was continued 1 hour.It is cooled to room temperature, is centrifuged after mixed solution is diluted with ethyl alcohol, use deionized water After repeatedly being washed with ethyl alcohol, 120-140 DEG C of drying is to get Na (Y1.5Na0.5)F6:Nd nanocrystals.

XRD spectrum shows that this material is hexagonal phase structure, consisting of Na (Y1.5Na0.5)F6:Nd(Fig. 3).Transmission electricity The micro- sem observation of son shows that interior nuclear particle is uniform nano spherical particle, and average grain diameter is 10 ~ 13 nm(Fig. 2).

Nd3+Have in 798 nm and 802 nm strongerf-fTransition absorption, can be with technology maturation in the market and cheap 800 nm semiconductor lasers match, substantially reduced when the material being made to be applied near infrared imaging the use of Image-forming instrument at This, is possibly realized for the extensive use of near infrared imaging.The exciting light of 800 nm is located at NIR I windows, has to biological tissue Preferable penetration capacity is easy to the living imaging of biological tissue.Nd3+'sf-fThe energy of transition absorption directly converts Nd3+'sf-fJump Transmitting light energy is moved, keeps its luminous efficiency higher.The phonon vibration energy of rare earth fluoride is relatively low, and the vibration for reducing material is quenched Sterilized journey keeps the luminous efficiency of material higher.Its most strong emission peak (1058 nm) is located at NIR II windows, to biological tissue Penetrability is more preferable, so as to more preferably realize the living imaging of biological tissue(Bibliography:1. Nature Materials, 2016, 15: 235-242. 2. ACS Nano, 2015, 9(12): 12255-12263.).

Embodiment two:Nucleocapsid Na (Y1.5Na0.5)F6:Nd @NaDyF4The preparation method of nano-particle.

6 mL oleic acid, 15 mL1- octadecylenes, 0.8 mmol sodium trifluoroacetates and 0.8 mmol trifluoroacetic acid dysprosiums are mixed equal It is even, the Na (Y of 0.8 mmol gained in embodiment one are then added1.5Na0.5)F6:Nd kernel nanocrystals, under nitrogen protection, It reacts 1 hour, is cooled to room temperature at a temperature of 280 DEG C.Centrifuged after mixed solution is diluted with ethyl alcohol, with deionized water and Ethyl alcohol is repeatedly after washing, and 120-140 DEG C of drying is to get Na (Y1.5Na0.5)F6:Nd @NaDyF4The nanocrystal of nucleocapsid.

XRD spectrum shows nucleocapsid Na (Y1.5 Na0.5)F6:Nd@NaDyF4Diffraction maximum and hexagonal phase structure NaDyF4XRD diffraction maximums it is consistent(Fig. 4), also with the Na (Y of hexagonal phase structure1.5 Na0.5)F6:The diffraction maximum of Nd is almost the same. The lattice structure of same core and the structure of shell are consistent, and the nano-particle of nucleocapsid is made more to stablize.Transmission electron microscopy Sem observation shows that the nano-particle of nucleocapsid is uniform nano spherical particle, and average grain diameter is 12 ~ 15 nm.It is coating NaDyF4After shell, pattern and the kernel Na (Y of the nano-particle of nucleocapsid1.5Na0.5)F6:The consistent appearance of Nd, it is only average Grain size increases 2 nm.Since the structure of kernel crystal and shell is almost the same, their lattice constant is close, so from TEM Apparent boundary is not seen(Fig. 2).The constituent content of this core-shell nano is measured with energy dispersion X-ray spectrum analysis (EDXA), it was confirmed that synthesized core-shell structure nanometer particle contains Y, the elements such as Nd, Dy(Fig. 5).

NaDyF4Shell has eliminated the defect of kernel particle surface, so that the luminous intensity of interior nuclear particle is increased 18%, together When NaDyF4With stronger paramagnetic performance, the nano-particle of nucleocapsid can obtain luminescence imaging simultaneously and contrast is higher Magnetic resonance imaging can realize biological tissue's living imaging of double mode with a kind of imaging agents, obtain more biological tissue's letters Breath.

The major advantage of material of the present invention has:

1. grain size and the distribution of shapes of converting core-shell structure nanometer particle under the near-infrared are uniform, grain size is small(12~15 nm), good dispersion, toxicity it is smaller.

2. being excited in infrared window I(The nm of 790 nm~810)It can be with cheap and technology maturation 800 nm Semiconductor laser matches, and the instrument use cost of near-infrared luminous imaging is made to be substantially reduced.

3. being excited in infrared window I, infrared window II luminescence imagings(Most strong emission peak is located at 1058 nm), in life Penetrability in object tissue is by force, it can be achieved that the live body luminescence imaging of biological tissue.

4. NaDyF4Shell makes kernel Na (Y1.5Na0.5)F6:The luminous intensity of r%Nd improves 18%, meanwhile, NaDyF4 Shell makes the nano-particle have stronger paramagnetic performance, makes the nano-particle that can obtain the biology with higher contrast simultaneously The magnetic resonance imaging of tissue(MR).With a kind of imaging agents, the imaging of double mode biological living is realized, obtain more biological tissue's letters Breath.

5. the stability of core-shell structure nanometer particle is very good, can be stored 6 months or more in 4 DEG C of refrigerators.

Claims (3)

1. a kind of near-infrared luminous core-shell structure nanometer particle, it is characterised in that the core-shell structure nanometer particle is with rare earth Close object Na (Y1.5Na0.5)F6:R%Nd is kernel, with NaDyF4Nanocrystal Na (the Y being made of shell1.5Na0.5)F6:R% Nd@NaDyF4, wherein r=5;The nanocrystal has hexagonal phase structure, and the average grain diameter of nanocrystal is 12~15nm, wherein The average grain diameter of kernel is 10~13nm.
2. near-infrared luminous core-shell structure nanometer particle according to claim 1, which is characterized in that the core-shell nano Particle is the spherical nucleocapsid that average grain diameter is 12~15nm.
3. a kind of method preparing near-infrared luminous core-shell structure nanometer particle according to claim 1 or 2, special Sign be this method the specific steps are:
A. the soluble-salt of rare earth ion is dissolved in oleic acid to be formed in transparent clear solution with 1- octadecylenes, adds sodium hydroxide With the methanol mixed solution of ammonium fluoride, be added in the soluble-salt of every gram of rare earth ion 0.09~0.12g sodium hydroxide and The ammonium fluoride of 0.135~0.155g under stirring, reacts 0.5~1.5 hour at 250~300 DEG C, and ethyl alcohol is added and isolates it again In solid product, be dispersed in organic polar solvent after washed, obtain Na (Y1.5Na0.5)F6:R%Nd kernels are nanocrystalline Body;
B. sodium trifluoroacetate and soluble dysprosium salt are dissolved in oleic acid with the mixed solution of 1- octadecylenes, step a institutes is then added The kernel nanocrystal obtained, wherein sodium trifluoroacetate, soluble dysprosium salt and the molar ratio of the kernel nanocrystal obtained by step a are 1:1:1 to 3:1:1, the methanol solution of ammonium fluoride is added, is reacted 1~3 hour at 260~300 DEG C, separation of ethanol is added and goes out solid-state Product obtains the nanocrystal Na (Y of the nucleocapsid after repeatedly washing1.5Na0.5)F6:R%Nd@NaDyF4, the fluorine The mass ratio for changing ammonium and sodium trifluoroacetate is 1:460.
CN201610478363.5A 2016-06-28 2016-06-28 Near-infrared luminous core-shell structure nanometer particle and preparation method thereof CN106085435B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610478363.5A CN106085435B (en) 2016-06-28 2016-06-28 Near-infrared luminous core-shell structure nanometer particle and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610478363.5A CN106085435B (en) 2016-06-28 2016-06-28 Near-infrared luminous core-shell structure nanometer particle and preparation method thereof

Publications (2)

Publication Number Publication Date
CN106085435A CN106085435A (en) 2016-11-09
CN106085435B true CN106085435B (en) 2018-10-23

Family

ID=57253075

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610478363.5A CN106085435B (en) 2016-06-28 2016-06-28 Near-infrared luminous core-shell structure nanometer particle and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106085435B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102925157A (en) * 2012-11-27 2013-02-13 哈尔滨工业大学 Preparation method of NaY(98-X)% F4:X%Yb, 2%Er@NaDyF4 in core-shell structure
CN101794834B (en) * 2009-12-14 2013-06-12 湖南共创光伏科技有限公司 High-efficiency thin-film solar cell provided with up-conversion fluorescent material film and film preparation method thereof
CN104232092A (en) * 2014-09-24 2014-12-24 上海大学 Zn<2+> sensitized rare earth up-conversion luminescent material and synthetic method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101794834B (en) * 2009-12-14 2013-06-12 湖南共创光伏科技有限公司 High-efficiency thin-film solar cell provided with up-conversion fluorescent material film and film preparation method thereof
CN102925157A (en) * 2012-11-27 2013-02-13 哈尔滨工业大学 Preparation method of NaY(98-X)% F4:X%Yb, 2%Er@NaDyF4 in core-shell structure
CN104232092A (en) * 2014-09-24 2014-12-24 上海大学 Zn<2+> sensitized rare earth up-conversion luminescent material and synthetic method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Novel upconversion phenomenon of Nd3+ sensitized by Yb3+ in Nd3+– Yb3+- co-dopedβ-Na(Y1. 5Na0.5)F6;Xiangfu Wang等;《Materials Letters》;20081231;第62卷;3865–3867 *
ynthesis and photoluminescent properties of α -NaYF4:Nd/α-NaYF4 core/shell nanostructure with enhanced near infrared (NIR) emission;Qiang Zhang等;《Materials Letters》;20091231;第63卷;376–378 *

Also Published As

Publication number Publication date
CN106085435A (en) 2016-11-09

Similar Documents

Publication Publication Date Title
Lecuyer et al. Chemically engineered persistent luminescence nanoprobes for bioimaging
Pandey et al. Improved luminescence and temperature sensing performance of Ho 3+–Yb 3+–Zn 2+: Y 2 O 3 phosphor
Zeng et al. PEG modified BaGdF5: Yb/Er nanoprobes for multi-modal upconversion fluorescent, in vivo X-ray computed tomography and biomagnetic imaging
Alam et al. Synthesis of carbon quantum dots from cabbage with down-and up-conversion photoluminescence properties: excellent imaging agent for biomedical applications
Zeng et al. Dual-modal upconversion fluorescent/X-ray imaging using ligand-free hexagonal phase NaLuF4: Gd/Yb/Er nanorods for blood vessel visualization
Yang et al. Cubic sub-20 nm NaLuF4-based upconversion nanophosphors for high-contrast bioimaging in different animal species
Cheng et al. Highly-sensitive multiplexed in vivo imaging using PEGylated upconversion nanoparticles
Li et al. Rare earth fluoride nano-/microcrystals: synthesis, surface modification and application
Tian et al. Self-assembled 3D flower-shaped NaY (WO 4) 2: Eu 3+ microarchitectures: microwave-assisted hydrothermal synthesis, growth mechanism and luminescent properties
Wong et al. Water dispersible ultra-small multifunctional KGdF 4: Tm 3+, Yb 3+ nanoparticles with near-infrared to near-infrared upconversion
Kobayashi et al. In vivo multiple color lymphatic imaging using upconverting nanocrystals
Zhao et al. Controlled synthesis, formation mechanism, and great enhancement of red upconversion luminescence of NaYF4: Yb3+, Er3+ nanocrystals/submicroplates at low doping level
Maldiney et al. In vivo optical imaging with rare earth doped Ca 2 Si 5 N 8 persistent luminescence nanoparticles
Zhang et al. Rare earth upconversion nanophosphors: synthesis, functionalization and application as biolabels and energy transfer donors
Wang et al. Down‐and Up‐Conversion Luminescent Nanorods
Qiu et al. Recent advances in lanthanide-doped upconversion nanomaterials: synthesis, nanostructures and surface modification
Mahalingam et al. Enhancing upconverted white light in Tm 3+/Yb 3+/Ho 3+-doped GdVO 4 nanocrystals via incorporation of Li+ ions
Zhang et al. Prevalence of anisotropic shell growth in rare earth core–shell upconversion nanocrystals
Mahalingam et al. Colloidal Tm3+/Yb3+‐doped LiYF4 nanocrystals: multiple luminescence spanning the UV to NIR regions via low‐energy excitation
Wang et al. NIR-induced highly sensitive detection of latent fingermarks by NaYF 4: Yb, Er upconversion nanoparticles in a dry powder state
Jaque et al. Inorganic nanoparticles for optical bioimaging
Chen et al. Aqueous one-pot synthesis of bright and ultrasmall CdTe/CdS near-infrared-emitting quantum dots and their application for tumor targeting in vivo
Zhang et al. Hydroxyapatite nano-and microcrystals with multiform morphologies: controllable synthesis and luminescence properties
Chatterjee et al. Upconversion fluorescence imaging of cells and small animals using lanthanide doped nanocrystals
Xu et al. Monodisperse core–shell structured up-conversion Yb (OH) CO3@ YbPO4: Er3+ hollow spheres as drug carriers

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant