CN108102641A - A kind of rare earth luminous nano material based on aggregation inducing effect and its preparation method and application - Google Patents
A kind of rare earth luminous nano material based on aggregation inducing effect and its preparation method and application Download PDFInfo
- Publication number
- CN108102641A CN108102641A CN201711351194.XA CN201711351194A CN108102641A CN 108102641 A CN108102641 A CN 108102641A CN 201711351194 A CN201711351194 A CN 201711351194A CN 108102641 A CN108102641 A CN 108102641A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- nano material
- inducing effect
- aggregation inducing
- preparation
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
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
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- 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
- 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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- 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
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
-
- 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
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
-
- 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
- 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"
- G01N2021/6432—Quenching
Abstract
The invention discloses a kind of rare earth luminous nano materials based on aggregation inducing effect and its preparation method and application.The rare earth luminous nano material based on aggregation inducing effect of the present invention is a kind of luminous coexisting materials of new rare earth luminous and aggregation inducing effect (AIE), which has homogeneous microscopic appearance, and grain diameter is about 32.16nm；The preparation method of the present invention is simple, oleophylic Rare Earth Europium Complex earth complex luminescent component is introduced rare earth luminous component is wrapped in nano-particle by the method for common assembling with compound A, and the aldehyde radical on surface can then react the surface that its modification is made to arrive particle with the amino of polyethyleneimine, the dispersiveness of the material in water is strong；The rare earth luminous nano material based on aggregation inducing effect of the present invention shows to detect behavior to hydrionic ratio fluorescent.It is used at least 10 times in addition, the detection process can be moved in circles by the pH of simple adjustment solution；It can be potential for the fields such as the detection of environment acidity and the imaging of cell soda acid.
Description
Technical field
The present invention relates to luminescent material technical field, more particularly to a kind of rare earth luminous nanometer based on aggregation inducing effect
Material and its preparation method and application.
Background technology
Fluorescence probe, since there is good biocompatibility, be readily synthesized and highly sensitive spatial and temporal resolution,
It is widely applied in bioanalysis, medical imaging, drug tracking etc., thus as the popular class of chemists
Topic.But traditional fluorescent material mostly there are a comparison it is serious the drawbacks of：Can only can just launch under solution state compared with
Strong fluorescence, but when the formation of aggregation or when being prepared into filminess, aggregation fluorescent quenching phenomenon is just inevitably sent out
It is raw.Since fluorescent material is coherent condition and form of film in a particular application, so aggregation inducing fluorescent quenching becomes organic
A great problem of the luminescent material in practical application, application field greatly reduce.Therefore, new organic fluorescent material is found to become
It obtains of crucial importance.
This loyalty of Tang in 2001 et al. is found that a kind of new compound, i.e. Silole during its experiment, this
Molecule does not observe apparent fluorescence under unimolecule state, can be showed when packing of molecules occurs into solid-state strong glimmering
Light, such phenomenon are also commonly referred to as aggregation-induced emission (AIE) effect.Has researcher's detailed analysis machine of the phenomenon
Reason, larger limitation will be subject to by showing that molecule is rotated and vibrated in the case where gathering state, so as to cause AIE phenomenons.
Somewhat different with some other luminophors, aggregation-induced emission (AIE) compound has the poly- of its uniqueness
This luminous species specificity efficiency of collection shows its stronger anti-concentration quenching effect that shines in the collected state；Moreover,
This compound also possesses some characteristics that response is generated to environmental stimuli, such as to temperature, pressure, albumen, biomolecule, quick-fried
The environmental stimulis such as fried object molecule, mould generate response.Unique AIE properties cause they structure high brightness fluorescent nano-particle,
Functional material and biological medicine application aspect have good prospect, thus cause the extensive interest of researchers and deep
Research.
Sweden chemist Lt.C.A.Arrhenius is found that " rare earth " element in a kind of black ore first within 1787.
So far from that time, rare earth element is to also belong to the 3rd from 15 elements of 57 to 7l and periodic table of atomic number
Two elements of yttrium that the scandium and atomic number that subgroup atomic number is 21 are 39 totally 17 elements gradually by chemist and
Physics worker has found, separates, purifies and probes into.It is since 4f electronics belongs to internal layer why rare earth compound, which can shine,
The electronics of track, electronics in the focusing among f-f configurations or among f-d configurations, due to the parity of rare earth ion prohibit it is existing
As, direct excitation rare-earth ion is difficult to obtain the transmitting of its characteristic fluorescence, however it is then allowed the absorption of two-photon, because
This, we are able to observe that different rare earth ions from UV, visible light until the full bands of a spectrum fluorescent emission of infrared region.
After the luminescent device of green fluorescence is made using the complex of rare earth terbium in nineteen ninety Kido etc., rare earth compound
Gradually start to be paid close attention to be subject to vast scientific research person in terms of electroluminescent, select suitable function organic ligand sensitization rare earth
Ionoluminescence and to prepare rare earth luminous complex be current research hotspot.The reason for one of them is critically important is since rare earth is sent out
Light can highly desirable utilize the energy of ligand triplet state, be conducive to enhance the efficiency of lighting component.Instantly rare earth coordination
It closes object and relatively broad concern is obtained in fields such as organic chemistry, fluoroscopic examination and embedded photoluminescent materials, just because of
These superior performances, make research rare earth complex compoud be just particularly important in terms of new and high technology luminescent material is sought.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of rare earth luminous nano material based on aggregation inducing effect and
Its preparation method and application, the preparation method of the rare earth luminous nano material is simple, and its dispersiveness in water is strong, photism
It can stablize, can be applied to the fields such as the detection of environment acidity and the imaging of cell soda acid.
In order to solve the above-mentioned technical problem, the technical scheme is that：
In a first aspect, a kind of preparation side of rare earth luminous nano material based on aggregation inducing effect provided by the invention
Method includes the following steps：
(1) offer or prepare compound A, the structure of the compound A is shown in formula I：
(2) by obtained by step (1) compound A, polyethyleneimine, oleophylic rare earth compounding respectively with the first organic solvent
Compound A solution, polyethylenimine solution, oleophylic rare earth compounding solution are obtained after being mixed to get, by Compound A solution and parent
Oily rare earth compounding solution is mixed to get mixture, then is added to after polyethylenimine solution is mixed with water in the mixture,
Rare earth luminous nano material is obtained by the reaction, wherein, the molar ratio of the compound A and the polyethyleneimine is 2~10:1；Institute
The molar ratio for stating compound A and the oleophylic rare earth compounding is 20~100:1.
Preferably, in the step (1), the compound A is to be made using following methods：
By 1,2,2- triphenyl -1- p-bromophenyls ethylene, 5- aldehyde radical -2- thienyl boric acids, four triphenyl phosphorus palladiums, second organic
Solvent mixing after, under conditions of inert gas shielding, in 100~130 DEG C be stirred to react 16~36 it is small when obtain crude product, will
The crude product separating-purifying obtains compound A, wherein, described 1,2,2- triphenyl -1- p-bromophenyls ethylene and 5- aldehyde radicals -2-
The molar ratio of thienyl boric acid is 1:1~2；Mole of the 1,2,2- triphenyls -1- p-bromophenyls ethylene and four triphenyl phosphorus palladiums
Than for 1:0.05~0.2.
It is further preferred that in the step (1), one kind in toluene, pyridine, benzene of second organic solvent or
It is several.
It is further preferred that in the step (1), the inert gas is selected from least one of nitrogen, argon gas.
It is further preferred that in the step (1), the extractant in dichloromethane, ethyl acetate at least one
Kind.
It is further preferred that in the step (1), the step of described " the crude product separating-purifying is obtained into compound A "
Suddenly, specifically include：
After the crude product is cooled down, stratification isolates organic layer, and the organic layer rotary evaporation removal of gained is had
The second organic solvent in machine layer is extracted 1~4 time using extractant, concentrated, be dried to obtain crude extract, is slightly carried described
After object, silica gel, lytic agent is taken to stir evenly, the silica gel dress column containing crude extract is obtained silica gel by re-evaporation removal lytic agent
Column, it is concentrated, be dried to obtain compound A using eluant, eluent to silicagel column elution 2~4 times.
Still more preferably, in the step (1), the mass ratio of the crude extract and silica gel is 0.5~2:10.
Still more preferably, in the step (1), the mass ratio of the lytic agent and the silica gel is 0.5~2:1.
Still more preferably, in the step (1), the lytic agent is selected from least one of toluene, ethyl acetate.
Still more preferably, in the step (1), the eluant, eluent is in petroleum ether, ethyl acetate, dichloromethane
It is any one or several.
Still more preferably, in the step (1), the eluant, eluent includes ether, ethyl acetate, wherein, the second
Ether, the volume ratio of ethyl acetate are 0.5~2:5.
Still more preferably, in the step (1), the dosage of the eluant, eluent is 50~100mL/ times.
Still more preferably, in the step (1), the eluant, eluent is 10~30 to the rate to silicagel column elution
Drop/min.
Preferably, in the step (2), first organic solvent is selected from least one of toluene, ethyl acetate.
Preferably, in the step (2), the rare earth element in the oleophylic rare earth compounding is europium, in dysprosium, terbium, cerium
It is one or more of.
It is further preferred that in the step (2), the rare earth element in the oleophylic rare earth compounding is europium.
Preferably, in the step (2), the oleophylic rare earth compounding is 4,4,4- tri- fluoro- 1-2- naphthalenes -1,3- of rare earth
Butanedione complex (RE (NTA)3), structural formula is as follows：
Wherein, RE is rare earth element.
It is further preferred that in the step (2), the oleophylic rare earth compounding for europium 4,4,4- tri- fluoro- 1-2- naphthalenes-
1,3- butanediones complex (Eu (NTA)3), structural formula is as follows：
Preferably, in the step (2), the molar ratio of the compound A and the polyethyleneimine is 5:1.
Preferably, in the step (2), the molar ratio of the compound A and the oleophylic rare earth compounding is 50:1.
Preferably, in the step (2), the condition of the reaction is：500~1500r/min of stir speed (S.S.) is (further excellent
Elect 800r/min as), mixing time is 3~15min (further preferably 5min).
Second aspect, a kind of rare earth luminous nano material based on aggregation inducing effect provided by the invention are using such as the
The preparation method of the rare earth luminous nano material based on aggregation inducing effect described in one side is made.
The third aspect, a kind of being received based on the rare earth luminous of aggregation inducing effect as described in second aspect provided by the invention
Application of the rice material in terms of acid-base value identification.
Fourth aspect, a kind of being received based on the rare earth luminous of aggregation inducing effect as described in second aspect provided by the invention
Application of the rice material in terms of cell soda acid imaging.
Compared with prior art, the beneficial effects of the present invention are：
(1) the rare earth luminous nano material based on aggregation inducing effect of the invention, be it is a kind of new rare earth luminous and
The luminous nano material coexisted of aggregation inducing effect (AIE), the material have homogeneous microscopic appearance, and grain diameter is about
32.16nm。
(2) preparation method of the invention is simple, introduces oleophylic Rare Earth Europium Complex earth complex luminescent component and passes through altogether with compound A
Rare earth luminous component is wrapped in nano-particle by the method for assembling, and the aldehyde radical on surface then can be with the amino of polyethyleneimine
Reaction makes its modification, and to the surface of particle, the dispersiveness of the material in water is by force.
(3) the rare earth luminous nano material the present invention is based on aggregation inducing effect shows to examine hydrionic ratio fluorescent
Survey behavior.When system is acidity, the blue-green fluorescent using ligand (having aggregation inducing effect) is leading, rare earth (europium) fluorescence
It quenches；When solution is in neutrality or during alkalescent, the red fluorescence of rare earth (europium) is leading, and the fluorescence of ligand then occurs centainly
Decrease.It is used at least 10 times in addition, the detection process can be moved in circles by the pH of simple adjustment solution；It potential can use
In the fields such as the detection of environment acidity and the imaging of cell soda acid.
Description of the drawings
Fig. 1 is the preparation flow figure of Study of Nanoscale Rare Earth Luminescent Materials provided by the present invention；
The nucleus magnetic hydrogen spectrum figure for the compound A that Fig. 2 is provided by the embodiment of the present invention 1；
The launching light spectrogram for the Study of Nanoscale Rare Earth Luminescent Materials that Fig. 3 is provided by the embodiment of the present invention 2；
The scanning electron microscope (SEM) photograph for the Study of Nanoscale Rare Earth Luminescent Materials that Fig. 4 is provided by the embodiment of the present invention 2；
The solution middle rare earth nano luminescent material in different hydrogen ion concentrations that Fig. 5 is provided for Application Example 1 of the present invention
The launching light spectrogram of material；
Fig. 6 is the Study of Nanoscale Rare Earth Luminescent Materials that Application Example 2 of the present invention is provided to hydrionic cycle detection curve.
Specific embodiment
The specific embodiment of the present invention is described further below in conjunction with the accompanying drawings.It should be noted that for
The explanation of these embodiments is used to help understand the present invention, but does not form limitation of the invention.It is in addition, disclosed below
The each embodiment of the present invention in involved technical characteristic can be combined with each other as long as they do not conflict with each other.
Embodiment 1
An embodiment of the present invention provides a kind of preparation methods of compound A, include the following steps：
In electronic analytical balance, the 1 of 500mg is weighed respectively with 100ml round-bottomed flasks, 2,2- triphenyl -1- are to bromobenzene
Base ethylene, the 5- aldehyde radical -2- thienyl boric acids of 217.95mg, tetra- triphenyl phosphorus palladiums of 140.463mg measure the carbon of 6.07ml with graduated cylinder
Sour potassium solution (10mM) is poured into wherein, adds in a certain amount of solvent toluene, then adds in suitable magneton, then nitrogen is passed through liquid
More than face air is emptied, open stirring+heat button, temperature is adjusted to 115 DEG C.When temperature rise reaches 115 DEG C, start
Timing, when the lower heating stirring reaction 24 of nitrogen protection is small, cooling, then contact plate, sees whether the reaction was complete, if instead with raw material comparison
Should be complete, it carries out in next step, the Separation ＆ Purification of product.Reaction mixture is poured into separatory funnel and carries out liquid separation, potassium carbonate
Layer separation, leaves organic layer, organic layer rotary evaporation drains organic solvent toluene and obtains solid.The solid ethyl acetate of gained
The extraction of 20ml water is added in after dissolving, collects organic phase and water phase, the water being collected into mutually extracts two respectively with 50ml ethyl acetate again
It is secondary, merge organic phase, rotary evaporation ware steams solvent and obtains crude product, by crude product and silica gel according to 1:10 mass ratio grinding
After mixing, after adding 1.5 times of the ethyl acetate dissolving that quality is silica gel quality, rotary evaporation removal organic solvent acetic acid second
After ester, dress column obtains silicagel column；60mL eluant, eluents is used to elute the silicagel column of gained with the drop speed of 15 drops/minute (to wash
De- agent is that ether and ethyl acetate with ratio are 1:5) the 3rd pipe contact plate, connect with test tube is through ZF-20D dark box type uv analyzers
It was found that product has gone out, concentration is collected, and revolving obtains pure products.
Structure and performance test：
(1) nucleus magnetic hydrogen spectrum figure detection is carried out to the product of 1 gained of the embodiment of the present invention, the results are shown in Figure 2, can by Fig. 2
Know,1H NMR(400MHz,CDCl3) δ 9.86 (s, 1H), 7.70 (d, J=3.9Hz, 1H), 7.42 (d, J=8.2Hz, 2H),
7.34 (d, J=3.9Hz, 1H), 7.18-6.98 (m, 17H), the structural formula of the product Compound A of 1 gained of the embodiment of the present invention is such as
Shown in Formulas I：
(2) embodiment of the present invention obtains the tetraphenyl ethylene that a kind of new thiophene aldehyde modifies using simple organic reaction and spreads out
Biologic artifact, i.e. compound A (compound shown in formula I), the compound have the property for significantly gathering induced luminescence.
The compound is dissolved in tetrahydrofuran, under the ultraviolet light of 365nm, observation finds solution almost without fluorescence；When the change
When closing object and being dissolved in the mixed liquor of tetrahydrofuran and deionized water, then it is able to observe that solution shows strong blue-green fluorescent.
Embodiment 2
An embodiment of the present invention provides a kind of preparation method of the rare earth luminous nano material based on aggregation inducing effect, bags
Include following steps：
Take compound A, polyethyleneimine (PEI), the Eu (NTA) of 1 gained of the embodiment of the present invention3, distinguished with tetrahydrofuran
Prepare Compound A solution TPE-S-CHO, polyethyleneimine (PEI) solution, Eu (NTA)3Solution, and respectively marked as 1. number, 2.
Number, 3. number, therefrom pipette 1ml concentration respectively with liquid-transfering gun as 1.0 × 10-2The 1. number solution of mol/L, concentration be 10mM 2. number
Solution, the 3. number solution that concentration is 1mM are denoted as sample 1, sample 2, sample 3 as mother liquor；Again mother liquor 1 is taken with liquid-transfering gun
Number 5uL is put into small test tube, then takes No. 3 1uL of mother liquor mixed mixtures 1 in small test tube；Mother liquor 2 is taken with liquid-transfering gun
1uL is put into small test tube, then takes 100uL distilled water is mixed in small test tube to obtain mixture 2；Mixture 2 is added to mixing
In object 1, magnetic agitation (800 revs/min) can obtain rapidly the suspended of rare earth luminous nano material in 5 minutes under normal temperature and pressure
Liquid, then high speed centrifugation, wash, be dried to obtain the rare earth luminous nano material of target.
In above-mentioned preparation method, in order to further improve the hydrophily of the rare earth luminous nano material of the present invention, and increase not
With shining for color, hydrophilic polymer P EI molecules and Rare Earth Europium Complex earth complex luminescent component are introduced, by rare earth luminous component bag
Inside nanoparticles are rolled in, and the aldehyde radical on surface can then react the surface that its modification is made to arrive particle with the amino of PEI, for increasing
The strong dispersiveness of material in water.
Performance test：
(1) Study of Nanoscale Rare Earth Luminescent Materials obtained by the embodiment of the present invention 2 is added in cuvette, and adds in deionization
Water, after which is disperseed in deionized water, under the ultraviolet light of 365nm, observation finds the solution
Show strong red fluorescence.
(2) using steady-state fluorescence spectrometer to the fluorescence light of the Study of Nanoscale Rare Earth Luminescent Materials obtained by the embodiment of the present invention 2
Spectrum is tested, and in the test of fluorescence spectrum, fixes its maximum excitation wavelength as 365nm, excitation and transmite slit width point
It Wei not 5.0nm, 5.0nm.
From Fig. 3 it is observed that being the fluorescent emission bands of a spectrum of compound shown in formula I positioned at the broad peak A of 510nm, and belong to
In blue light region；And the emission peak that B, C, D, E, F are indicated is then corresponding to rare-earth europium ion5D0It arrives7FJ(J=0,1,2,3,4)
Distinctive energy level transition peak, wherein, emission peak (D) luminous intensity at 618nm is maximum, and belongs to red light district.
(3) the microcosmic nanotopography of rare earth luminous composite material is observed using projection electron microscope, is observed
The results are shown in Figure 4.
As shown in figure 4, rare earth luminescent material shows smaller nano-scale, with its particle of apparatus measures the results show
Footpath is about 32.16 nanometers, and shows more regular decentralized particle.
Application Example 1
In order to further illustrate beneficial effects of the present invention, the step of according to Examples 1 to 2, obtained rare earth nano shines
Material, it is spare.The hydrogen chloride solution of various concentration is respectively configured, concentration is respectively：10-7mol/L、10-6mol/L、10-5mol/
L、10-4mol/L、10-3Then each 1mL of the hydrogen chloride solution of above-mentioned various concentration, ratio is transferred to liquid-transfering gun by mol/L respectively
In color ware, and it is respectively labeled as 1. number, 2. number, 3. number, 4. number, 5. number；It is dispersed to by the Study of Nanoscale Rare Earth Luminescent Materials of gained
In water, its concentration in water is made to obtain the solution containing Study of Nanoscale Rare Earth Luminescent Materials for 100mg/L；It will be contained with liquid-transfering gun again
The solution 10uL for having Study of Nanoscale Rare Earth Luminescent Materials be transferred to respectively 1. number, 2. number, 3. number, 4. number, 5. in number cuvette, finally,
Its fluorescence spectrum is detected, test result is as shown in Figure 5.
As shown in Figure 5, detection finds that the fluorescence of rare earth shows and subtracts after we add in hydrogen ion (HCl) into system
Weak trend, and broad peak A then occurs to enhance phenomenon, and with H+Concentration continue to increase, the fluorescent emission of rare earth gradually subtracts
It is small until almost disappear, and the fluorescence of the rare earth luminous nano material of present invention gained then shows becoming of constantly enhancing
Gesture.The weak variation of the last one one of different emission bands enables us to significantly observe that the fluorescence of system has feux rouges to become blue
The process of green light, i.e. ratio fluorescent detection process.
Application Example 2
Investigate a kind of quality of fluorescent sensing material, it will usually which can be related to the material can for the detection of guest molecule
With indexs such as reuse and service efficiencies.Therefore, in order to further illustrate beneficial effects of the present invention, according to embodiment 1
Study of Nanoscale Rare Earth Luminescent Materials is made in~2 the step of, spare；It and will be by adjusting the pH of solution come the change of fluorescence in observation system
Change.
Measure 100mL deionized water into beaker, and by the Study of Nanoscale Rare Earth Luminescent Materials of gained be dispersed to it is above-mentioned go from
In sub- water, the solution containing Study of Nanoscale Rare Earth Luminescent Materials is obtained, then, the pH value of solution is adjusted to 3.0 using concentrated hydrochloric acid, with shifting
The above-mentioned solution of 1mL is transferred in cuvette by liquid rifle, measures its luminous intensity respectively using Fluorescence Spectrometer；Hydroxide is used again
After the pH of solution in beaker is adjusted to neutral (pH value 7.0) by sodium, the above-mentioned solution of 1mL is transferred in cuvette with liquid-transfering gun,
Measure its luminous intensity respectively using Fluorescence Spectrometer；It repeats the above steps 10 times, takes most strong emission spectrum pair at 615nm
The relative intensity of fluorescence answered is with reference to mapping, obtains measurement result as shown in Figure 6.
It will be appreciated from fig. 6 that find Study of Nanoscale Rare Earth Luminescent Materials repeatedly test after 10 cycle after, fluorescence intensity is almost
Do not decay significantly, it was demonstrated that the material can repeatedly use.
Embodiment 3
An embodiment of the present invention provides a kind of preparation method of the rare earth luminous nano material based on aggregation inducing effect, bags
Include following steps：
(1) preparation of compound A：In electronic analytical balance, the 1 of 500mg, 2 are weighed respectively with 100ml round-bottomed flasks,
2- triphenyl -1- p-bromophenyls ethylene, the 5- aldehyde radical -2- thienyl boric acids of 190.28mg, tetra- triphenyl phosphorus palladiums of 140.463mg are used
The solution of potassium carbonate 10mM that graduated cylinder measures 6.07ml is poured into wherein, is added in a certain amount of solvent toluene, is then added in suitable magnetic
Son, then nitrogen is passed through more than liquid level and empties air, stirring+heat button is opened, temperature is adjusted to 100 DEG C.Treat that temperature raises
When reaching 100 DEG C, start timing, when the lower heating stirring reaction 36 of nitrogen protection is small, cooling, then contact plate, sees with raw material comparison
Whether the reaction was complete, if the reaction was complete, carries out in next step, the Separation ＆ Purification of product.Reaction mixture is poured into separatory funnel
Liquid separation is carried out, potassium carbonate layer is separated, leaves organic layer, organic layer rotary evaporation drains organic solvent toluene.Solid acetic acid
Ethyl ester dissolving and then addition 20ml water extractions, water are mutually extracted twice respectively with 50ml ethyl acetate again, and organic phase is collected in concentration, is revolved
Turn evaporating dish and steam solvent to obtain crude product, by crude product and silica gel according to 1:After 20 quality is than ground and mixed, matter is added
After measuring 0.5 times of the ethyl acetate dissolving for silica gel quality, after rotary evaporation removal organic solvent ethyl acetate, dress column obtains silicon
Rubber column gel column；40mL eluant, eluents is used to be eluted using the drop speed of 10 drops/minute to the silicagel column of gained, and (eluant, eluent is ether and acetic acid
Ethyl ester is 0.5 with ratio:5), find that product has gone out through ZF-20D dark box types uv analyzer with the 3rd pipe contact plate that test tube connects,
Concentration is collected, and revolving obtains compound A.
(2) compound A, polyethyleneimine (PEI), the Eu (NTA) obtained by step (1) are taken3, prepared respectively with tetrahydrofuran
Polyethyleneimine (PEI) solution, the Eu (NTA) of 1mM of Compound A solution TPE-S-CHO, 10mM of 10mM3Solution, and respectively
Marked as 1. number, 2. number, 3. number, concentration is therefrom pipetted respectively with liquid-transfering gun as 1.0 × 10-21. number solution, the concentration of mol/L is
The 2. number solution of 10mM, concentration are 3. each 1mL of number solution of 1mM, and are denoted as No. 3 sample 1, sample 2, sample conducts respectively
Mother liquor；With liquid-transfering gun No. 1 2uL of mother liquor is taken to be put into small test tube again, then take No. 3 1uL of mother liquor are mixed in small test tube must mix
Close object 1；With liquid-transfering gun No. 2 1uL of mother liquor is taken to be put into small test tube, then take 100uL distilled water is mixed in small test tube must mix
Close object 2；Mixture 2 is added in mixture 1, and magnetic agitation (500 revs/min) can obtain rapidly for 10 minutes under normal temperature and pressure
The suspension of rare earth luminous nano material, then high speed centrifugation, wash, be dried to obtain the rare earth luminous nano material of target.
Embodiment 4
An embodiment of the present invention provides a kind of preparation method of the rare earth luminous nano material based on aggregation inducing effect, bags
Include following steps：
(1) preparation of compound A：In electronic analytical balance, the 1 of 500mg, 2 are weighed respectively with 100ml round-bottomed flasks,
2- triphenyl -1- p-bromophenyls ethylene, the 5- aldehyde radical -2- thienyl boric acids of mg, tetra- triphenyl phosphorus palladiums of 140.463mg, with graduated cylinder amount
The solution of potassium carbonate (10mM) of 6.07ml is taken to pour into wherein, adds in a certain amount of solvent toluene, then adds in suitable magneton, then
Nitrogen is passed through more than liquid level and empties air, stirring+heat button is opened, temperature is adjusted to 130 DEG C.Treat that temperature rise reaches
At 130 DEG C, start timing, when the lower heating stirring reaction 160 of nitrogen protection is small, cooling, then contact plate, with raw material comparison see whether
The reaction was complete, if the reaction was complete, carries out in next step, the Separation ＆ Purification of product.Reaction mixture is poured into separatory funnel to carry out
Liquid separation separates potassium carbonate layer, leaves organic layer, organic layer rotary evaporation drains organic solvent toluene.Solid ethyl acetate
Dissolving and then addition 20ml water extractions, water are mutually extracted twice respectively with 50ml ethyl acetate again, and organic phase is collected in concentration, is rotated and is steamed
Hair ware steams solvent and obtains crude product, by crude product and silica gel according to 1:After 5 quality is than ground and mixed, quality is added as silicon
After 2 times of the ethyl acetate dissolving of colloid amount, after rotary evaporation removal organic solvent ethyl acetate, dress column obtains silicagel column；It adopts
Eluted that (eluant, eluent is matched somebody with somebody as ether and ethyl acetate to the silicagel column of gained with 100mL eluant, eluents using the drop speed of 20 drops/minute
Ratio is 0.5:5), with crude product, through silica gel column chromatography, (eluant, eluent is that ether and ethyl acetate with ratio are 1:5) separate, test tube
The 3rd pipe contact plate connect finds that product has gone out through ZF-20D dark box types uv analyzer, and concentration is collected, and revolving obtains compound A.
(2) compound A, polyethyleneimine (PEI), the Eu (NTA) obtained by step (1) are taken3, prepared respectively with tetrahydrofuran
Polyethyleneimine (PEI) solution, the 1mM Eu (NTA) of Compound A solution TPE-S-CHO, 10mM of 10mM3Solution, and respectively
Marked as 1. number, 2. number, 3. number, concentration is therefrom pipetted respectively with liquid-transfering gun as 1.0 × 10-21. number solution, the concentration of mol/L is
The 2. number solution of 10mM, concentration are 3. each 1mL of number solution of 1mM, and are denoted as No. 3 sample 1, sample 2, sample conducts respectively
Mother liquor；With liquid-transfering gun No. 1 10uL of mother liquor is taken to be put into small test tube again, then take No. 3 1uL of mother liquor are mixed in small test tube must mix
Close object 1；With liquid-transfering gun No. 2 1uL of mother liquor is taken to be put into small test tube, then take 100uL distilled water is mixed in small test tube must mix
Close object 2；Mixture 2 is added in mixture 1, and magnetic agitation (1500 revs/min) can obtain rapidly for 3 minutes under normal temperature and pressure
The suspension of rare earth luminous nano material, then high speed centrifugation, wash, be dried to obtain the rare earth luminous nano material of target.
Embodiments of the present invention are explained in detail above in association with attached drawing, but the invention is not restricted to described implementations
Mode.For a person skilled in the art, in the case where not departing from the principle of the invention and spirit, to these embodiments
A variety of change, modification, replacement and modification are carried out, are still fallen in protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the rare earth luminous nano material based on aggregation inducing effect, which is characterized in that including walking as follows
Suddenly：
(1) offer or prepare compound A, the structure of the compound A is shown in formula I：
(2) compound A, polyethyleneimine, the oleophylic rare earth compounding obtained by step (1) are mixed respectively with the first organic solvent
Compound A solution, polyethylenimine solution, oleophylic rare earth compounding solution are obtained after obtaining, Compound A solution is dilute with oleophylic
Native complex solution is mixed to get mixture, then is added to after polyethylenimine solution is mixed with water in the mixture, reaction
Rare earth luminous nano material is obtained, wherein, the molar ratio of the compound A and the polyethyleneimine is 2~10:1；Describedization
The molar ratio for closing object A and the oleophylic rare earth compounding is 20~100:1.
2. the preparation method of the rare earth luminous nano material according to claim 1 based on aggregation inducing effect, feature
It is, in the step (1), the compound A is to be made using following methods：
By 1,2,2- triphenyl -1- p-bromophenyls ethylene, 5- aldehyde radical -2- thienyl boric acids, four triphenyl phosphorus palladiums, the second organic solvent
After mixing, under conditions of inert gas shielding, in 100~130 DEG C be stirred to react 16~36 it is small when obtain crude product, will described in
Crude product separating-purifying obtains compound A, wherein, described 1,2,2- triphenyl -1- p-bromophenyls ethylene and 5- aldehyde radical -2- thiophene
The molar ratio of boric acid is 1:1~2；The molar ratio of the 1,2,2- triphenyls -1- p-bromophenyls ethylene and four triphenyl phosphorus palladiums is
1:0.05~0.2.
3. the preparation method of the rare earth luminous nano material according to claim 2 based on aggregation inducing effect, feature
It is, in the step (1), second organic solvent is selected from one or more of toluene, pyridine, benzene.
4. the preparation method of the rare earth luminous nano material according to claim 2 based on aggregation inducing effect, feature
It is, in the step (1), the inert gas is selected from least one of nitrogen, argon gas.
5. the preparation method of the rare earth luminous nano material according to claim 2 based on aggregation inducing effect, feature
It is, in the step (1), the extractant is selected from least one of dichloromethane, ethyl acetate.
6. the preparation method of the rare earth luminous nano material according to claim 1 based on aggregation inducing effect, feature
It is, in the step (2), the rare earth element in the oleophylic rare earth compounding is one or more of europium, dysprosium, terbium, cerium.
7. the preparation method of the rare earth luminous nano material according to claim 1 based on aggregation inducing effect, feature
It is, in the step (2), the oleophylic rare earth compounding is matched somebody with somebody for 4,4,4- tri- fluoro- 1-2- naphthalenes -1,3- butanediones of rare earth
Close object (RE (NTA)3), structural formula is as follows：
Wherein, RE is rare earth element.
8. a kind of rare earth luminous nano material based on aggregation inducing effect, which is characterized in that be using such as claim 1~8
The preparation method of rare earth luminous nano material of any one of them based on aggregation inducing effect is made.
It is 9. a kind of as claimed in claim 8 based on the rare earth luminous nano material of aggregation inducing effect in terms of acid-base value identification
Application.
10. a kind of be imaged as claimed in claim 8 based on the rare earth luminous nano material of aggregation inducing effect in cell soda acid
The application of aspect.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711351194.XA CN108102641B (en) | 2017-12-15 | 2017-12-15 | Rare earth luminescent nano material based on aggregation induction effect and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711351194.XA CN108102641B (en) | 2017-12-15 | 2017-12-15 | Rare earth luminescent nano material based on aggregation induction effect and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108102641A true CN108102641A (en) | 2018-06-01 |
| CN108102641B CN108102641B (en) | 2020-01-21 |
Family
ID=62216396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711351194.XA Expired - Fee Related CN108102641B (en) | 2017-12-15 | 2017-12-15 | Rare earth luminescent nano material based on aggregation induction effect and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108102641B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004510A (en) * | 2014-04-29 | 2014-08-27 | 中山大学 | Organic luminescent material simultaneously having piezoluminescence and aggregation-induced luminescence properties, and synthesis method and application thereof |
-
2017
- 2017-12-15 CN CN201711351194.XA patent/CN108102641B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004510A (en) * | 2014-04-29 | 2014-08-27 | 中山大学 | Organic luminescent material simultaneously having piezoluminescence and aggregation-induced luminescence properties, and synthesis method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| KAZUHIRO ANDO ET AL.: "High-performance fluorescent particles prepared via miniemulsion polymerization", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| YING-CHEN DUAN ET AL.: "Influence of Aggregation on the Structure and Fluorescent Properties of a Tetraphenylethylene Derivative: a Theoretical Study", 《CHEM PHYS CHEM》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108102641B (en) | 2020-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Carbon dots: synthesis, formation mechanism, fluorescence origin and sensing applications | |
| Guan et al. | Bismuth-MOF based on tetraphenylethylene derivative as a luminescent sensor with turn-off/on for application of Fe3+ detection in serum and bioimaging, as well as emissive spectra analysis by TRES | |
| Xu et al. | Fabrication and application of a ratiometric and colorimetric fluorescent probe for Hg 2+ based on dual-emissive metal–organic framework hybrids with carbon dots and Eu 3+ | |
| Lv et al. | Development of film sensors based on conjugated polymers for copper (II) ion detection | |
| Liu et al. | Tetrathienylethene based red aggregation-enhanced emission probes: super red-shifted mechanochromic behavior and highly photostable cell membrane imaging | |
| Wang et al. | Terbium hybrid particles with spherical shape as luminescent probe for detection of Cu2+ and Fe3+ in water | |
| CN106916159B (en) | A kind of switch nanometer porphyrin fluorescence sensor controllable method for preparing | |
| CN106957243A (en) | A kind of copper ion detection probe based on aggregation-induced emission and its preparation method and application | |
| Li et al. | Chemical sensing failed by aggregation-caused quenching? A case study enables liquid/solid two-phase determination of N2H4 | |
| CN107290316A (en) | A kind of tetracycline fluorescence new detecting method based on zirconium base MOF | |
| Sun et al. | A turn-off fluorescent probe for the detection of copper (II) ion based on a salicylaldehyde derivatives Schiff-base | |
| CN113105349B (en) | Luminescent compound with aggregation induction and supermolecule polymerization fluorescent nano material and preparation method thereof | |
| CN106478458B (en) | Schiff base compound and its preparation method and application based on tetraphenylethylene and Maleic nitrile | |
| Zhang et al. | A FRET-based fluorescent probe for mercury ions in water and living cells | |
| Yan et al. | Aggregation-induced emission enhancement (AIEE)-active boron-difluoride dyes with reversible mechanochromic fluorescence | |
| Sun et al. | Sensitive and selective urinary 1-hydroxypyrene detection by dinuclear terbium-sulfonylcalixarene complex | |
| Du et al. | A sTable 3D Cd (ii) metal–organic framework for highly sensitive detection of Cu 2+ ions and nitroaromatic explosives | |
| Wu et al. | Construction of carbon dots/metal–organic framework composite for ratiometric sensing of norfloxacin | |
| CN108329910A (en) | A kind of graphene oxide grafting 8-hydroxyquinoline fluorescent composition and its intercalation layered double-hydroxide fluorescence composite material | |
| CN110194951A (en) | Tetraphenyl ethylene derivatives fluorescent probe and preparation method thereof | |
| Zhou et al. | Carbon dots-based modularization fluorescent probe for simultaneous detection of Hg2+ and Cu2+ in water, cells and zebrafish | |
| CN111303862B (en) | Double-emission fluorescent temperature-sensitive polymer composite film and preparation method and application thereof | |
| CN108102641A (en) | A kind of rare earth luminous nano material based on aggregation inducing effect and its preparation method and application | |
| CN113651821B (en) | Derivative fluorescent probe based on pyrrolopyrroledione and application thereof | |
| CN108752266A (en) | Triphenylamine base AIE fluorescence probes and its synthetic method containing terpyridyl and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200121 Termination date: 20201215 |