CN107828408A - The lower conversion nano fluorescence probe of the window of near-infrared second transmitting and its synthetic method - Google Patents
The lower conversion nano fluorescence probe of the window of near-infrared second transmitting and its synthetic method Download PDFInfo
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- CN107828408A CN107828408A CN201710945844.7A CN201710945844A CN107828408A CN 107828408 A CN107828408 A CN 107828408A CN 201710945844 A CN201710945844 A CN 201710945844A CN 107828408 A CN107828408 A CN 107828408A
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- 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
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- 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
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
Abstract
The invention belongs to nano meter biomaterial technical field, conversion nano fluorescence probe and its synthetic method under the specially a kind of window of near-infrared second transmitting.Fluorescence probe of the present invention includes inertia stratum nucleare, lower conversion centre of luminescence shell, energy transmission shell and energy absorption shell；Inertia stratum nucleare is used for the size for adjusting overall nanocrystal；The lower rare earth nano crystal changed the centre of luminescence and adulterated into active ions；Energy transmission layer is used for the energy transmission of absorption to the centre of luminescence, and by changing the thickness of energy transmission layer relaxation time for extending or shortening light emitting ionic, and then the fluorescence lifetime of nanocrystalline fluorescence probe is changed, realize the controllable and adjustable of fluorescence lifetime；Energy-absorbing layer is used to absorb extraneous exciting light.The present invention can be used for the lower multiple signaling molecules of in situ detection simultaneously of deep tissue, further improves the sensitivity and the degree of accuracy of detection, has broad application prospects in protein expression, biological sample high flux screening, multichannel Biological Detection etc..
Description
Technical field
The invention belongs to nano meter biomaterial technical field, and in particular to a kind of life-span adjustable window of near-infrared second hair
Penetrate lower conversion nano fluorescence probe and its synthetic method.
Background technology
Nowadays imaging technique has become the measuring means of medical diagnosis standard, with the development of science and technology, medical science into
While becoming more and more accurate as technology, it is also desirable to more specifically biological characteristic is provided, so as to help we to disease
Intuitivism apprehension, and the screening to treatment method, more specifically foundation is provided for therapeutic evaluation.Fluorescence imaging due in real time,
Noninvasive, high-resolution and the advantages of Multiple detection can be realized using wavelength, in life science and biological technical field
It has been widely used Deng field.In past research, what researchers mainly studied is the fluorescence imaging of visible light wave range,
Have very strong absorption and scattering in this wave band yet with biological tissue so that internal fluoroscopic examination difficult to realize and into
Picture.And recent study work shows, relative to visible ray and near infrared light first window（700 nm -900 nm）Light come
Say, light of the biological tissue to the window of near-infrared second（1000 nm-1700 nm）There are the absorption and scattering of very little, therefore can be with
It is greatly enhanced image quality and penetration depth so that the light in the second window of near-infrared section is more for the imaging of deep tissue biological
Prospect.Because bioanalysis, medical diagnosis on disease and biological medicine research field need the more information of albumen and gene target identification,
And Multiple detection realizes the fast signal identification of nucleic acid and albumen, but the probe for widely using VISIBLE LIGHT EMISSION at present is realized
Multiple detection can not expand to the window region of near-infrared second well.It can currently realize that the window region of near-infrared second is launched
Fluorescence probe such as single-walled carbon nanotube, quantum dot and organic fluorescent dye etc. suffer from wider emission peak, detection process
Easily overlapped between middle different spectrum, which greatly limits the quantity of sense channel.And restrict deep tissue Multiple detection more
Main cause comes from organism different tissues to the absorption coefficient of different wave length and the difference of scattering coefficient, so that it cannot
Realize the quantization of internal Multiple detection.
Transition material can also realize the transmitting of the window region of near-infrared second under rare earth, and have higher luminous effect
Rate, narrower emission peak, less photobleaching, longer fluorescence lifetime and relatively low long term toxicity etc., it is to be used for deep organize
A kind of very promising fluorescence probe of Multiple detection.But due to lower transition material doping rare earth ion absorption cross-section and
Difference between level-density parameter, the emission effciency of different rare earth ions have very big difference.Due to compared to spectrum, fluorescence lifetime
Independent of light intensity and tissue penetration depths, and narrow distribution range, seem more there is robust in the presence of ambient noise
Property.If can be using rare earth longer fluorescence lifetime the characteristics of, realize that fluorescence lifetime is adjustable by some structure designs, then
The lower conversion nano particle of this life-span adjustable window of near-infrared second transmitting, it will be multiple inspection under a kind of preferably deep tissue
Fluorescence probe is surveyed, has broader practice in terms of bioanalysis and disease detection.
The content of the invention
It is simple, adjustable near available for the deep life-span for organizing Multiple detection it is an object of the invention to provide a kind of preparation technology
Conversion nano fluorescence probe and its synthetic method under infrared second window transmitting.
The lower conversion nano fluorescence probe of the window of life-span tunable near-infrared second transmitting provided by the invention, is a kind of core three
The nanocrystal of shell structurre, inertia stratum nucleare, lower conversion centre of luminescence shell, energy transmission shell and energy are followed successively by from inside to outside
Amount absorbs shell.Wherein, inertia stratum nucleare is used for the size for adjusting overall nanocrystal；It is lower to change the centre of luminescence and mixed into active ions
Miscellaneous rare earth nano crystal；Energy transmission layer is used for the energy transmission of absorption to the centre of luminescence；Energy-absorbing layer is used to absorb
Extraneous exciting light.The present invention is changed by changing rare earth ion doped species and doping in nanocrystal building-up process
Lower switching emission wavelength, then by changing the thickness of energy transmission layer relaxation time for extending or shortening light emitting ionic, enter
And the fluorescence lifetime of nanocrystalline fluorescence probe is changed, the controllable and adjustable of fluorescence lifetime is realized, can be obtained a series of
The lower conversion nano fluorescence probe of different fluorescence lifetimes under near-infrared the second window region different emission and single wavelength.
In the present invention, the size of described inert core is 2-200nm, and the lower thickness for changing centre of luminescence shell is 0.4-
300 nm, energy transmission shell thickness are 0-300 nm（Preferably 0.4-300 nm）, energy absorption shell thickness is 0.4-300
nm。
In the present invention, described inertia stratum nucleare is made up of matrix；Its host material is selected from fluoride：CaF2、BaF2、LaF3、
YF3、ZnF2、NaYF4、NaYbF4、LiYF4、KYF4、NaGdF4Or NaLuF4；It is glimmering that inertia stratum nucleare is used to adjust finally lower conversion nano
The size of light probe.
In the present invention, the described lower conversion centre of luminescence is made up of matrix, sensitized ions and active ions；Wherein, matrix
For NaReF4、LiReF4、KReF4Or BaReF5, Re Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,
One or more in Yb, Lu；Sensitized ions are Yb3+；The molar content of sensitized ions is 0.01% ~ 99.9%；Active ions are
Ce3+、Pr3+、Sm3+、Eu3+、Tb3+、Dy3+、Er3+、Tm3+、Ho3+In one or several kinds；The molar content of active ions is
0.01%~30%；
In the present invention, described energy transmission layer is made up of matrix and sensitized ions；Wherein, matrix NaReF4、LiReF4、
KReF4Or BaReF5, one kind or several in Re Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
Kind；Sensitized ions are Yb3+；The molar content of sensitized ions is 0% ~ 100%（It is preferred that the molar content of sensitized ions is 5% ~ 95%）；
Fluorescence lifetime is adjusted by adjusting the thickness of energy transmission layer；Energy transmission thickness degree can since 0 nm continuously adjustabe；
In the present invention, described energy-absorbing layer is made up of matrix and sensitized ions；Wherein, matrix NaReF4、LiReF4、
KReF4Or BaReF5, one kind or several in Re Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
Kind；Sensitized ions are Nd3+, Yb3+In it is one or two kinds of；The molar content of sensitized ions is 0.01% ~ 60%.
The present invention provides the synthetic method of the lower conversion nano fluorescence probe of the above-mentioned window of life-span tunable near-infrared second transmitting,
Comprise the following steps that：
（1）The preparation of shell presoma：
A, the preparation of lower conversion centre of luminescence presoma：Rare-earth salts is dissolved among high boiling solvent under vacuum；
Wherein, rare-earth salts is selected from：Chloride, nitrate, acetate, oxide, trifluoroacetate, acetylacetonate；Comprising matrix
Rare earth element is Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu；Comprising sensitizer rare earth member
Element is Yb；Comprising active ions rare earth element be Ce, Pr, Sm, Eu, Tb, Dy, Ho, Er, Tm in one or more；Height boiling
Point solvent is selected from：In oleic acid, stearic acid, capric acid, laurate, myristic acid, palmitic acid, octadecylene, atoleine, olive oil
It is one or several kinds of；Solution temperature is 20-150 degrees Celsius；The concentration of final resulting solution is 0.01 mol/L-5 mol/L；
B, the preparation of energy transmission layer presoma：Rare-earth salts is dissolved among high boiling solvent under vacuum；Wherein,
Rare-earth salts is selected from：Chloride, nitrate, acetate, oxide, trifluoroacetate, acetylacetonate；Comprising matrix rare earth member
Element is Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu；Comprising sensitizer rare earth element be Yb；
High boiling solvent is selected from：Oleic acid, stearic acid, capric acid, laurate, myristic acid, palmitic acid, octadecylene, atoleine, olive oil
In one or several kinds；Solution temperature is 20-150 degrees Celsius；The concentration of final resulting solution is 0.01 mol/L-5 mol/
L；
C, the preparation of energy-absorbing layer presoma：Rare-earth salts is dissolved among high boiling solvent under vacuum；Wherein,
Rare-earth salts is selected from：Chloride, nitrate, acetate, oxide, trifluoroacetate, acetylacetonate；Comprising matrix rare earth member
Element is Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu；Comprising sensitizer rare earth element for Yb,
It is one or two kinds of in Nd；High boiling solvent is selected from：Oleic acid, stearic acid, capric acid, laurate, myristic acid, palmitic acid, ten
One or several kinds in eight alkene, atoleine, olive oil；Solution temperature is 20-150 degrees Celsius；Finally resulting solution is dense
Spend for 0.01 mol/L-5 mol/L；
D, the preparation of sodium trifluoroacetate/potassium/lithium/barium solution：By sodium trifluoroacetate or trifluoroacetic acid potassium or trifluoroacetic acid lithium or three
Fluoroacetic acid barium, is dissolved in high boiling solvent；High boiling solvent is：Oleic acid, stearic acid, capric acid, laurate, myristic acid, palm fibre
One or several kinds in palmitic acid acid, octadecylene, atoleine, olive oil；Solution temperature is 20-150 degrees Celsius, obtains solution note
For sodium trifluoroacetate/potassium/lithium/barium solution；The concentration of final resulting solution is 0.01 mol/L-5 mol/L；
（2）The synthesis of inert core：Oleic acid, oleyl amine, trioctylphosphine, octadecylene, atoleine are used as high-temperature solvent, rare earth
Raw material uses rare earth-iron-boron, rare earth trifluoroacetate, rare earth nitrades or lanthanon acetate；Reactant should also include fluorination
One or several kinds in ammonium, sodium fluoride, lithium fluoride, potassium fluoride, sodium hydroxide, potassium hydroxide, lithium hydroxide；In 200-320
Degree Celsius, react under nitrogen atmosphere, reaction time 5-180 min, obtain the preferably lower conversion rare earth of dispersiveness and uniformity and receive
Meter Jing Ti, as inert core；
（3）The preparation of lower conversion centre of luminescence shell：Using the lower rare earth nano crystal of changing prepared in previous step into nucleus,
Under the conditions of 150-340 celsius temperatures, two kinds of shell precursor solutions are continuously alternatively introduced into, incorporation way is dropwise addition；Draw every time
The volume ratio that centre of luminescence presoma and sodium trifluoroacetate/potassium/lithium/barium solution are converted under the higher boiling entered is 10:1 to 1:
10；Lower conversion centre of luminescence shell is made outside inert core, is designated as@shells 1；
（4）The preparation of energy transmission shell：Using prepared in previous step core, the structure nano crystal of shell 1 as nucleus, in 150-340
Under the conditions of celsius temperature, two kinds of shell precursor solutions are continuously alternatively introduced into, incorporation way is dropwise addition；Higher boiling is introduced every time
The volume ratio of energy transmission layer presoma and sodium trifluoroacetate/potassium/lithium/barium solution is 10:1 to 1:10；It is made outside@shells 1
Energy transmission shell, it is designated as@shells 2；
（5）The preparation of energy absorption shell：Using the core, shell 1, the structure nano crystal of shell 2 prepared in previous step as nucleus,
Under the conditions of 150-340 celsius temperatures, two kinds of shell precursor solutions are continuously alternatively introduced into, incorporation way is dropwise addition；Draw every time
The volume ratio for entering higher boiling energy-absorbing layer presoma and sodium trifluoroacetate/potassium/lithium/barium solution is 10:1 to 1:10；In@shells
Energy absorption shell is made outside 2, is designated as@shells 3.
In the present invention, the thickness of shell can be determined by the way that the amount of precursor solution is added dropwise.
In the present invention, different luminescent center ions is added by controlling, regulation obtains the different window regions of near-infrared second
The lower transition material of transmitting；Pass through the regulation to energy transmission thickness degree（More than the nm of adjustable extent 0 of thickness, usually 0-
300nm）, obtain different fluorescence lifetimes under single wavelength.For example, when holmium is light emitting ionic, fluorescence emission peak is 1155 nm,
When energy transmission thickness degree is 0-7 nm, fluorescence lifetime is 0.4-0.92 ms.When bait is light emitting ionic, fluorescence emission peak is
1525 nm, when energy transmission thickness degree is 0-7 nm, fluorescence lifetime is 1.2-7.2 ms.
Nano-crystal with core-shell structure body synthesized by the present invention（The fluorescence probe of Single wavelength transmitting）, finally realize 808
Under nm exciting lights, 1064 nm, 1155 nm, five 1289 nm, 1475 nm and 1525 nm wave bands Single wavelength transmitting, the life-span
Adjustable range is 0.4-7.2 ms.
The present invention can be changed by changing rare earth ion doped species and doping in nanocrystal building-up process
Lower switching emission wavelength, then by adjusting the thickness of energy transmission layer, change the fluorescence lifetime under single wavelength, obtaining the life-span can
Adjust the lower conversion nano fluorescence probe of the window of near-infrared second transmitting.The present invention can simultaneously the multiple signaling molecules of in situ detection, enter
One step improves the sensitivity and the degree of accuracy of detection.The present invention fluorescence probe protein expression, biological sample high flux screening,
Multichannel Biological Detection and medical diagnosis on disease etc. have broad application prospects.
Brief description of the drawings
Fig. 1 is that 808 nm near-infrareds excite, the knot of the life-span adjustable window region of near-infrared second transmitting fluorescent nano material
Structure schematic diagram.
Fig. 2 is prepared NaGdF4@NaGdF4:Yb/ Er(18/2 %)@NaYF4:Yb(10%)@ NaNdF4:Yb
(10%) the brilliant transmission electron microscope photo of conversion nano under.
Fig. 3 is prepared NaGdF4@NaYbF4:Ho(15 %)@NaYF4:Yb(10%)@ NaNdF4:Lower turn of Yb (10%)
Change the nanocrystalline fluorescence spectra in the case where 808 nm near infrared lights excite.
Fig. 4 is prepared NaGdF4@NaYbF4:Ho(15 %)@NaYF4:Yb(10%)@ NaNdF4:Lower turn of Yb (10%)
The nanocrystalline fluorescence lifetime figure under 1155 nm near infrared emissions is changed, wherein, curve 1 represents that the thickness of energy transmission layer is 0
Nm, the thickness of 2 expression energy transmission layers is 3.6 nm, and the thickness of 3 expression energy transmission layers is 7.2 nm.
Fig. 5 is prepared NaGdF4@NaGdF4:Yb/ Er(18/2 %)@NaYF4:Yb(10%)@ NaNdF4:Yb
(10%) fluorescence spectra of the conversion nano crystalline substance in the case where 808 nm near infrared lights excite under.
Fig. 6 is prepared NaGdF4@NaGdF4:Yb/ Er(18/2 %)@NaYF4:Yb(10%)@ NaNdF4:Yb
(10%) fluorescence lifetime figure of the conversion nano crystalline substance under 1525 nm near infrared emissions under.Wherein, curve 1 represents energy transmission thickness
Spend for 0 nm, the thickness of 2 expression energy transmission layers be 0.9 nm, and the thickness of 3 expression energy transmission layers is 7.2 nm.
Label in figure：1 is lower conversion centre of luminescence shell, and 2 be energy transmission shell, and 3 be energy absorption shell.
Embodiment
Embodiment 1：
NaGdF4@NaYbF4:Ho(15 %)@NaYF4:Yb(10%)@ NaNdF4:The nm of the second window of Yb (10%) near-infrared 1155
The brilliant preparation of the lower conversion nano of transmitting.Comprise the following steps that：
（1）The preparation of shell presoma.Gd-OA（0.1 M）The preparation of presoma：100 mL three neck round bottom flask are taken to hold for reaction
Device, sequentially add 2.5 mmol GdCl3, 10 mL oleic acid（OA）, 15 mL octadecylenes（ODE）.In vacuum and magnetic agitation bar
140 degrees Celsius are heated under part and is kept for 1 hour, finally gives the Gd-OA of clear（0.1 M）Presoma.
Yb, Ho-OA（0.1 M）The preparation of presoma：It is reaction vessel to take 50 mL three neck round bottom flask, is sequentially added
2.5 mmol ReCl3(Re:85% Yb, 15% Ho), 10 mL oleic acid（OA）, 15 mL octadecylenes（ODE）.In vacuum and
140 degrees Celsius are heated under the conditions of magnetic agitation and is kept for 1 hour, finally gives the Gd, Yb, Er-OA of clear（0.1
M）Presoma.
Y, Yb-OA（0.1 M）The preparation of presoma：It is reaction vessel to take 50 mL three neck round bottom flask, sequentially adds 2.5
mmol ReCl3(Re:90% Y, 10% Yb), 10 mL oleic acid（OA）, 15 mL octadecylenes（ODE）.Stirred in vacuum and magnetic force
140 degrees Celsius are heated under the conditions of mixing and is kept for 1 hour, finally gives the Y, Yb-OA of clear（0.1 M）Presoma.
Nd, Yb-OA（0.1 M）The preparation of presoma：It is reaction vessel to take 50 mL three neck round bottom flask, is sequentially added
2.5 mmol ReCl3(Re:90% Nd, 10% Yb), 5 mL oleic acid（OA）, 20 mL octadecylenes（ODE）.In vacuum and magnetic
140 degrees Celsius are heated under power stirring condition and is kept for 1 hour, finally gives the Y, Yb-OA of clear（0.1 M）Forerunner
Body.
The preparation of Na-TFA-OA presomas：It is reaction vessel to take 25 mL three neck round bottom flask, sequentially adds 4 mmol tri-
Fratol and 10 mL oleic acid, the room-temperature dissolution under vacuum and stirring condition, before obtaining the Na-TFA-OA of water white transparency clarification
Drive liquid solution.
（2）NaGdF4The synthesis of lower conversion nano nucleus
It is reaction vessel to take 100 mL three neck round bottom flask, is firstly added 2.0 mmol GdCl3；Then add 12 mL oleic acid
（OA）, 30 mL octadecylenes（ODE）.Reactant is heated with stirring to 140 DEG C, vacuum dehydration deoxidation 30 minutes, finally given
Bright mixed solution.By 5 mmol NaOH and 8 mmol NH4F, which is dissolved in, mixes and injects above-mentioned reaction in 10mL methanol solutions
Reacted in solution.After continuously stirring 2 hours, reactant is warming up under high-purity argon gas protection with 10 DEG C/min speed
Insulation reaction 90 minutes after 280 DEG C.Ethanol is added after reactant is cooled into 50 DEG C makes product Precipitation from solution, then
Centrifugation, product is obtained after being washed 3-5 times repeatedly using absolute ethyl alcohol.
（3）NaGdF4@NaYbF4:The synthesis of conversion nano nucleus under Ho (15 %)
Take the above-mentioned purification liquid of 5 mL（~ 0.5 mmol）In 8 mL oleic acid（OA）, 12 mL octadecylenes（ODE）It is mixed and heated to
70 degrees Celsius, 30 minutes hexamethylenes and oxygen removed in reaction system are kept under vacuum.Then by reaction system with
20 DEG C/min speed is warming up to 280 degrees Celsius.Then mL Yb, the Ho-OA presomas of alternate dropwise addition 1 and 0.5 into reaction bulb
ML Na-TFA-OA presomas.The interval time being added dropwise every time is 15 minutes.Number, which is added dropwise, to be entered according to the needs of shell thickness
Row adjustment.Adding ethanol after question response terminates, after reaction mother liquor is cooled into 50 DEG C makes product Precipitation from solution, then
Centrifugation, obtains product after being washed 3-5 times repeatedly using absolute ethyl alcohol, and product is dissolved in standby in 5 mL hexamethylenes.
（4）NaGdF4@NaYbF4:Ho(15 %)@NaYF4:The brilliant synthesis of Yb (10%) core-shell nano
Take the above-mentioned purification liquid of 5 mL（~ 0.5 mmol）In 8 mL oleic acid（OA）, 12 mL octadecylenes（ODE）It is mixed and heated to
70 degrees Celsius, 30 minutes hexamethylenes and oxygen removed in reaction system are kept under vacuum.Then by reaction system with
20 DEG C/min speed is warming up to 280 degrees Celsius.Then mL Y, the Yb-OA presomas of alternate dropwise addition 1 and 0.5 into reaction bulb
ML Na-TFA-OA presomas.The interval time being added dropwise every time is 15 minutes.Number, which is added dropwise, to be entered according to the needs of shell thickness
Row adjustment.Adding ethanol after question response terminates, after reaction mother liquor is cooled into 50 DEG C makes product Precipitation from solution, then
Centrifugation, obtains product after being washed 3-5 times repeatedly using absolute ethyl alcohol, and product is dissolved in standby in 5 mL hexamethylenes.
（5）NaGdF4@NaYbF4:Ho(15 %)@NaYF4:Yb(10%)@ NaNdF4:The brilliant conjunction of Yb (10%) core-shell nano
Into
Take the above-mentioned purification liquid of 5 mL（~ 0.5 mmol）In 4 mL oleic acid（OA）, 16 mL octadecylenes（ODE）It is mixed and heated to
70 degrees Celsius, 30 minutes hexamethylenes and oxygen removed in reaction system are kept under vacuum.Then by reaction system with
20 DEG C/min speed is warming up to 280 degrees Celsius.Then mL Nd, the Yb-OA presomas of alternate dropwise addition 1 and 0.5 into reaction bulb
ML Na-TFA-OA presomas.The interval time being added dropwise every time is 15 minutes.Number, which is added dropwise, to be entered according to the needs of shell thickness
Row adjustment.Adding ethanol after question response terminates, after reaction mother liquor is cooled into 50 DEG C makes product Precipitation from solution, then
Centrifugation, obtains product after being washed 3-5 times repeatedly using absolute ethyl alcohol, and product is dissolved in standby in 5 mL hexamethylenes.
Prepared fluorescence probe size is 12-30 nm, oil-soluble, under 808 nm exciting lights, emission band 1100-
1200 nm, fluorescence lifetime of the peak wavelength in 1155 nm are 0.4-0.92 ms.
Embodiment 2：
NaGdF4@NaGdF4:Yb/ Er(18/2 %)@NaYF4:Yb(10%)@ NaNdF4:Yb (10%) second window of near-infrared
The brilliant preparation of the lower conversion nano of 1525 nm transmittings.Comprise the following steps that：
（1）The preparation of shell presoma.Gd-OA（0.1 M）The preparation of presoma：100 mL three neck round bottom flask are taken to hold for reaction
Device, sequentially add 2.5 mmol GdCl3, 10 mL oleic acid（OA）, 15 mL octadecylenes（ODE）.In vacuum and magnetic agitation bar
140 degrees Celsius are heated under part and is kept for 1 hour, finally gives the Gd-OA of clear（0.1 M）Presoma.
Gd, Yb, Er-OA（0.1 M）The preparation of presoma：It is reaction vessel to take 50 mL three neck round bottom flask, is added successively
Enter 2.5 mmol ReCl3(Re:80% Gd, 18% Yb, 2% Er), 10 mL oleic acid（OA）, 15 mL octadecylenes（ODE）.
140 degrees Celsius are heated under the conditions of vacuum and magnetic agitation and is kept for 1 hour, finally gives Gd, the Yb of clear,
Er-OA（0.1 M）Presoma.
Y, Yb-OA（0.1 M）The preparation of presoma：It is reaction vessel to take 50 mL three neck round bottom flask, sequentially adds 2.5
mmol ReCl3(Re:90% Y, 10% Yb), 10 mL oleic acid（OA）, 15 mL octadecylenes（ODE）.Stirred in vacuum and magnetic force
140 degrees Celsius are heated under the conditions of mixing and is kept for 1 hour, finally gives the Y, Yb-OA of clear（0.1 M）Presoma.
Nd, Yb-OA（0.1 M）The preparation of presoma：It is reaction vessel to take 50 mL three neck round bottom flask, is sequentially added
2.5 mmol ReCl3(Re:90% Nd, 10% Yb), 5 mL oleic acid（OA）, 20 mL octadecylenes（ODE）.In vacuum and magnetic
140 degrees Celsius are heated under power stirring condition and is kept for 1 hour, finally gives the Y, Yb-OA of clear（0.1 M）Forerunner
Body.
The preparation of Na-TFA-OA presomas：It is reaction vessel to take 25 mL three neck round bottom flask, sequentially adds 4 mmol tri-
Fratol and 10 mL oleic acid, the room-temperature dissolution under vacuum and stirring condition, before obtaining the Na-TFA-OA of water white transparency clarification
Drive liquid solution.
（2）NaGdF4The synthesis of lower conversion nano nucleus
It is reaction vessel to take 100 mL three neck round bottom flask, is firstly added 2.0 mmol GdCl3；Then add 12 mL oleic acid
（OA）, 30 mL octadecylenes（ODE）.Reactant is heated with stirring to 140 DEG C, vacuum dehydration deoxidation 30 minutes, finally given
Bright mixed solution.By 5 mmol NaOH and 8 mmol NH4F, which is dissolved in, mixes and injects above-mentioned reaction in 10mL methanol solutions
Reacted in solution.After continuously stirring 2 hours, reactant is warming up under high-purity argon gas protection with 10 DEG C/min speed
Insulation reaction 90 minutes after 280 DEG C.Ethanol is added after reactant is cooled into 50 DEG C makes product Precipitation from solution, then
Centrifugation, product is obtained after being washed 3-5 times repeatedly using absolute ethyl alcohol.
（3）NaGdF4@NaGdF4:The synthesis of conversion nano nucleus under Yb/ Er (18/2 %)
Take the above-mentioned purification liquid of 5 mL（~ 0.5 mmol）In 8 mL oleic acid（OA）, 12 mL octadecylenes（ODE）It is mixed and heated to
70 degrees Celsius, 30 minutes hexamethylenes and oxygen removed in reaction system are kept under vacuum.Then by reaction system with
20 DEG C/min speed is warming up to 280 degrees Celsius.Then mL Gd, Yb, the Er-OA presomas of alternate dropwise addition 1 into reaction bulb
With 0.5 mL Na-TFA-OA presomas.The interval time being added dropwise every time is 15 minutes.Number is added dropwise can be according to shell thickness
Need to be adjusted.Adding ethanol after question response terminates, after reaction mother liquor is cooled into 50 DEG C makes product precipitate analysis from solution
Go out, then centrifugation, obtains product after being washed 3-5 times repeatedly using absolute ethyl alcohol, and product is dissolved in standby in 5 mL hexamethylenes
With.
（4）NaGdF4@NaGdF4:Yb/ Er(18/2 %)@NaYF4:The brilliant synthesis of Yb (10%) core-shell nano
Take the above-mentioned purification liquid of 5 mL（~ 0.5 mmol）In 8 mL oleic acid（OA）, 12 mL octadecylenes（ODE）It is mixed and heated to
70 degrees Celsius, 30 minutes hexamethylenes and oxygen removed in reaction system are kept under vacuum.Then by reaction system with
20 DEG C/min speed is warming up to 280 degrees Celsius.Then mL Y, the Yb-OA presomas of alternate dropwise addition 1 and 0.5 into reaction bulb
ML Na-TFA-OA presomas.The interval time being added dropwise every time is 15 minutes.Number, which is added dropwise, to be entered according to the needs of shell thickness
Row adjustment.Adding ethanol after question response terminates, after reaction mother liquor is cooled into 50 DEG C makes product Precipitation from solution, then
Centrifugation, obtains product after being washed 3-5 times repeatedly using absolute ethyl alcohol, and product is dissolved in standby in 5 mL hexamethylenes.
（5）NaGdF4@NaGdF4:Yb/ Er(18/2 %)@NaYF4:Yb(10%)@ NaNdF4:Yb (10%) core-shell nano
Brilliant synthesis
Take the above-mentioned purification liquid of 5 mL（~ 0.5 mmol）In 4 mL oleic acid（OA）, 16 mL octadecylenes（ODE）It is mixed and heated to
70 degrees Celsius, 30 minutes hexamethylenes and oxygen removed in reaction system are kept under vacuum.Then by reaction system with
20 DEG C/min speed is warming up to 280 degrees Celsius.Then mL Nd, the Yb-OA presomas of alternate dropwise addition 1 and 0.5 into reaction bulb
ML Na-TFA-OA presomas.The interval time being added dropwise every time is 15 minutes.Number, which is added dropwise, to be entered according to the needs of shell thickness
Row adjustment.Adding ethanol after question response terminates, after reaction mother liquor is cooled into 50 DEG C makes product Precipitation from solution, then
Centrifugation, obtains product after being washed 3-5 times repeatedly using absolute ethyl alcohol, and product is dissolved in standby in 5 mL hexamethylenes.
Prepared fluorescence probe size is 12-30 nm, oil-soluble, under 808 nm exciting lights, emission band 1450-
1650 nm, fluorescence lifetime of the peak wavelength in 1525 nm are 1.2-7.2 ms.
Claims (4)
1. the lower conversion nano fluorescence probe of a kind of life-span adjustable window of near-infrared second transmitting, it is characterised in that be one kind one
The nanocrystal of the shell structurre of core three, inertia stratum nucleare, lower conversion centre of luminescence shell, energy transmission shell are followed successively by from inside to outside
With energy absorption shell；Wherein, inertia stratum nucleare is used for the size for adjusting overall nanocrystal；It is lower conversion the centre of luminescence for activation from
The rare earth nano crystal of son doping；Energy transmission layer is used for the energy transmission of absorption to the centre of luminescence；Energy-absorbing layer is used for
Absorb extraneous exciting light；By changing rare earth ion doped species and doping in nanocrystal building-up process, under change
Switching emission wavelength, then by changing the thickness of energy transmission layer relaxation time for extending or shortening light emitting ionic, and then
The fluorescence lifetime of nanocrystalline fluorescence probe is changed, realizes the controllable and adjustable of fluorescence lifetime；
The size of described inert core is 2-200nm, and the lower thickness for changing centre of luminescence shell is 0.4-300 nm, energy transmission
Thickness degree is 0-300 nm, and energy-absorbing layer thickness is 0.4-300 nm；
Described inertia stratum nucleare is made up of matrix；Host material is selected from fluoride：CaF2、BaF2、LaF3、YF3、ZnF2、NaYF4、
NaYbF4、LiYF4、KYF4、NaGdF4Or NaLuF4；
The described lower conversion centre of luminescence is made up of matrix, sensitized ions and active ions；Wherein, host material is selected from NaReF4、
LiReF4、KReF4Or BaReF5, in Re Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
It is one or more of；Sensitized ions are Yb3+；The molar content of sensitized ions is 0.01% ~ 99.9%；Active ions are Ce3+、Pr3+、
Sm3+、Eu3+、Tb3+、Dy3+、Er3+、Tm3+、Ho3+In one or several kinds；The molar content of active ions is 0.01% ~ 30%；
Described energy transmission layer is made up of matrix and sensitized ions；Wherein, host material is selected from NaReF4、LiReF4、KReF4
Or BaReF5, the one or more in Re Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu；
Sensitized ions are Yb3+；The molar content of sensitized ions is 0% ~ 100%；
Described energy-absorbing layer is made up of matrix and sensitized ions；Wherein, host material is selected from NaReF4、LiReF4、KReF4
Or BaReF5, the one or more in Re Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu；It is quick
Change ion is Nd3+、Yb3+In it is one or two kinds of；The molar content of sensitized ions is 0.01% ~ 60%.
2. the lower conversion nano fluorescence probe of the life-span adjustable window of near-infrared second transmitting according to claim 1, it is special
Sign is that under 808 nm exciting lights the second window of near-infrared emission band is 1064 nm, 1155 nm, 1289 nm, 1475
Nm and 1525 nm；Fluorescence lifetime is 1 μ s ~ 10ms.
A kind of 3. lower conversion nano fluorescence probe of the life-span as claimed in claim 1 or 2 adjustable window of near-infrared second transmitting
Synthetic method, it is characterised in that comprise the following steps that：
（1）The preparation of shell presoma：
A, the preparation of lower conversion centre of luminescence presoma：Rare-earth salts is dissolved among high boiling solvent under vacuum；
Wherein, rare-earth salts is selected from：Chloride, nitrate, acetate, oxide, trifluoroacetate, acetylacetonate；Comprising matrix
Rare earth element is Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu；Comprising sensitizer rare earth member
Element is Yb；Comprising active ions rare earth element be Ce, Pr, Sm, Eu, Tb, Dy, Ho, Er, Tm in one or more；Height boiling
Point solvent is selected from：In oleic acid, stearic acid, capric acid, laurate, myristic acid, palmitic acid, octadecylene, atoleine, olive oil
It is one or several kinds of；Solution temperature is 20-150 degrees Celsius；The concentration of final resulting solution is 0.01 mol/L-5 mol/L；
B, the preparation of energy transmission layer presoma：Rare-earth salts is dissolved among high boiling solvent under vacuum；Wherein,
Rare-earth salts is selected from：Chloride, nitrate, acetate, oxide, trifluoroacetate, acetylacetonate；Comprising matrix rare earth member
Element is Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu；Comprising sensitizer rare earth element be Yb；
High boiling solvent is selected from：Oleic acid, stearic acid, capric acid, laurate, myristic acid, palmitic acid, octadecylene, atoleine, olive oil
In one or several kinds；Solution temperature is 20-150 degrees Celsius；The concentration of final resulting solution is 0.01 mol/L-5 mol/
L；
C, the preparation of energy-absorbing layer presoma：Rare-earth salts is dissolved among high boiling solvent under vacuum；Wherein,
Rare-earth salts is selected from：Chloride, nitrate, acetate, oxide, trifluoroacetate, acetylacetonate；Comprising matrix rare earth member
Element is Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu；Comprising sensitizer rare earth element for Yb,
It is one or two kinds of in Nd；High boiling solvent is selected from：Oleic acid, stearic acid, capric acid, laurate, myristic acid, palmitic acid, ten
One or several kinds in eight alkene, atoleine, olive oil；Solution temperature is 20-150 degrees Celsius；Finally resulting solution is dense
Spend for 0.01 mol/L-5 mol/L；
D, the preparation of sodium trifluoroacetate/potassium/lithium/barium solution：By sodium trifluoroacetate or trifluoroacetic acid potassium or trifluoroacetic acid lithium or three
Fluoroacetic acid barium, is dissolved in high boiling solvent；High boiling solvent is：Oleic acid, stearic acid, capric acid, laurate, myristic acid, palm fibre
One or several kinds in palmitic acid acid, octadecylene, atoleine, olive oil；Solution temperature is 20-150 degrees Celsius, obtains solution note
For sodium trifluoroacetate/potassium/lithium/barium solution；The concentration of final resulting solution is 0.01 mol/L-5 mol/L；
（2）The synthesis of inert core：Oleic acid, oleyl amine, trioctylphosphine, octadecylene, atoleine are used as high-temperature solvent, rare earth
Raw material uses rare earth-iron-boron, rare earth trifluoroacetate, rare earth nitrades or lanthanon acetate；Reactant should also include fluorination
One or several kinds in ammonium, sodium fluoride, lithium fluoride, potassium fluoride, sodium hydroxide, potassium hydroxide, lithium hydroxide；In 200-320
Degree Celsius, react under nitrogen atmosphere, reaction time 5-180 min, obtain the preferably lower conversion rare earth of dispersiveness and uniformity and receive
Meter Jing Ti, as inert core；
（3）The preparation of lower conversion centre of luminescence shell：Using the lower rare earth nano crystal of changing prepared in previous step into nucleus,
Under the conditions of 150-340 celsius temperatures, two kinds of shell precursor solutions are continuously alternatively introduced into, incorporation way is dropwise addition；Draw every time
Centre of luminescence presoma is changed under the higher boiling entered with the volume ratio of sodium trifluoroacetate/potassium/lithium/barium solution as 10:1 to 1:
10；Lower conversion centre of luminescence shell is made outside inert core, is designated as@shells 1；
（4）The preparation of energy transmission shell：Using prepared in previous step core, the structure nano crystal of shell 1 as nucleus, in 150-340
Under the conditions of celsius temperature, two kinds of shell precursor solutions are continuously alternatively introduced into, incorporation way is dropwise addition；Higher boiling is introduced every time
The volume ratio of energy transmission layer presoma and sodium trifluoroacetate/potassium/lithium/barium solution is 10:1 to 1:10；It is made outside@shells 1
Energy transmission shell, it is designated as@shells 2；
（5）The preparation of energy absorption shell：Using the core, shell 1, the structure nano crystal of shell 2 prepared in previous step as nucleus,
Under the conditions of 150-340 celsius temperatures, two kinds of shell precursor solutions are continuously alternatively introduced into, incorporation way is dropwise addition；Draw every time
The volume ratio for entering higher boiling energy-absorbing layer presoma and sodium trifluoroacetate/potassium/lithium/barium solution is 10:1 to 1:10；In@shells
Energy absorption shell is made outside 2, is designated as@shells 3.
4. the synthesis of the lower conversion nano fluorescence probe of the life-span adjustable window of near-infrared second transmitting according to claim 3
Method, it is characterised in that the thickness of shell is adjusted by the way that the amount of precursor solution is added dropwise.
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