CN108504348A - A kind of preparation and application of double fluorescent polymer quanta point materials - Google Patents
A kind of preparation and application of double fluorescent polymer quanta point materials Download PDFInfo
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- CN108504348A CN108504348A CN201810283888.2A CN201810283888A CN108504348A CN 108504348 A CN108504348 A CN 108504348A CN 201810283888 A CN201810283888 A CN 201810283888A CN 108504348 A CN108504348 A CN 108504348A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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
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Abstract
The invention discloses a kind of double fluorescent polymer quanta point materials to be covalently joined together by the hydrophobic TPE blues chromophore with AIE properties and amphiphilic PNIPAM, the polymer quantum dot TPE monoPNIPAM of nano-scale can be self-assembled into, TPE monoPNIPAM Eu (III) are made by the coordination with Eu (III), which has double fluorescent characteristic, aggregation-induced emission characteristic, temperature-sensitives well.To Hela cell dyeings the result shows that, the polymer quantum dot can well dye cytoplasm, aggregation highlights fluorescence to generate in cytoplasm, blue and red complex light can be generated under different excitation wavelengths, bright blue light can be especially generated when 365nm is excited, highlighted feux rouges is generated when 395nm is excited, and can preferably be applied in biological field, such as cell imaging, cell tracker.
Description
Technical field
The present invention relates to a kind of preparation of polymer quantum dot more particularly to a kind of double fluorescent polymer quanta point materials
It prepares；Double fluorescent polymer quanta point materials can be assembled in Hela cytoplasm and show highlighted fluorescence, thus can be used as
Cell tracker agent etc. is preferably applied in biological field.
Background technology
Polymer quantum dot（Polymer Dots）Be it is a kind of prepared by polymer material it is organic with fluorescent effect
Fluorescent nano particles, it is different from inorganic semiconductor quantum dot, has stronger fluorescent brightness, more stable optical characteristics, shape
Many advantages, such as looks are controllable.Polymer quantum dot is generally not only with hydrophily end but also with lipophile end, the energy in water-oil systems
Self assembly enough occurs.Tetraphenyl ethylene is a kind of typical aggregation photoluminescence（AIE）Lipophile small molecule, in weak solution, four
Styrene molecules show " propeller " formula structure, and intermolecular interaction is smaller, and four phenyl can in the space being respectively staggered
It significantly vibrates, the vibration aggravation of intramolecular bond, a large amount of energy are consumed in the form of infrared radiant energy when energized, fluorescence
Intensity is weaker.When in state of aggregation or solid, the intermolecular overlapped extruding of phenyl ring, intramolecular phenyl ring rotation space weakens or disappears
It loses, the vibration of key also weakens, and molecule is forced to give off energy in the form of fluorescence by non-radiative, generates very strong fluorescence.Four
For styrene as a kind of luminous organic molecule of intense blue, processing hands in many fields such as dyestuff, fluoroscopic examination, cell imaging can
Heat.
Poly(N-isopropylacrylamide) (PNIPAM) is a kind of water-soluble linear polymer of Thermo-sensitive, and molecule includes
There are a certain proportion of hydrophobic and hydrophilic functional groups, when being dissolved in water phase, their intramolecular, intermolecular generation phase interactions with water
With due to the effect of hydrogen bond and Van der Waals force, the hydrone around macromolecular chain can form one layer by hydrogen bond connection, ordering
The higher water phase shell of degree, in low temperature, the interaction of PNIPAM and water is mainly the interaction of amide group and water,
When the temperature increases, intramolecular, intermolecular hydrophobic effect are reinforced, and the interaction parameter between PNIPAM and water occurs prominent
Become, form hydrophobic layer, part hydrogen bond destroys, and hydrone shows as phase transformation from solvated layer discharge, generates Thermo-sensitive, minimum to face
Ranging from 31 ~ 33 DEG C of boundary solution temperature LCST, very narrow phase transformation range makes it be answered extensively in fields such as drug release, biological developings
With.The PNIPAM of the tetraphenyl ethylene of highlighted fluorescence and Thermo-sensitive is covalently attached so that become a kind of novel Thermo-sensitive
Highlighted fluorescent material, her openr application field.But in cell imaging, many organelles and albumen will produce green
Background fluorescence, seriously affected application and development of this material in biological field, therefore develop and a kind of there are double fluorescence volumes
The cell dyeing material of son point material is extremely urgent.
In the recent period, the compound of europium is due to high brightness, narrow half-peak breadth, larger Stokes shift and longer smooth service life
Etc. attracting wide attention, correspondingly, multiduty europium compound is able to extensive use in various fields, including thin as detection
The detection agent of intracellular environment, the protein tag of living cells imaging, enzyme analysis etc..Contain a large amount of amido bond on PNIPAM long-chains,
Coordination well can occur with rare earth elements europium, this europium complex will produce the colour purity of 610 ~ 620nm receiving the when of exciting
The very high red fluorescence of degree, can be good at penetrating background signal and being detected in cell imaging, this by different excitations
And good application prospect will be had in field of biology by generating the prodigious double fluorescent materials of two kinds of aberration.
Invention content
The object of the present invention is to provide a kind of preparation methods of double fluorescent polymer quanta point materials；
It is a further object of the present invention to provide double fluorescent polymer quanta point materials for the dyeability of cell and as thin
The application of born of the same parents' tracer.
One, the preparation of double fluorescent polymer quanta point materials
（1）4- hydroxyphenyl ethylene（TPE-monoOH）Preparation
With tetrahydrofuran（THF）For solvent, zinc powder is reducing agent, TiCl4Catalyst, under protection of argon gas, 4- hydroxy benzophenones
Ketone and benzophenone are with 1:1~1:2 molar ratio, at 70 ~ 75 DEG C flow back 20 ~ for 24 hours；It is cooled to room temperature, is added after answering
K2CO3Aqueous solution quenching reaction, ethyl acetate extraction, revolving drying, obtains the crude product of brown color；Crude product crosses silica gel chromatograph
Post separation, first phosphor dot are 4- hydroxyphenyl ethylene（TPE-monoOH）；
The addition of zinc powder be 4- dihydroxy benaophenonels, 0.5 ~ 1.5 times of benzophenone integral molar quantity；
TiCl4Addition be 4- dihydroxy benaophenonels, 1.5 ~ 2 times of benzophenone integral molar quantity.
（2）The preparation of initiator TPE-AZO
By 4- hydroxyphenyl ethylene（TPE-monoOH）With azo -4,4 '-dicyano glutaric acid（ACVA）It is dissolved in tetrahydrofuran
（THF）In, add 4-dimethylaminopyridine（DMAP, catalyst）And dicyclohexylcarbodiimide（DCC, dehydrating agent）, argon gas
Protection, react 20 in 70 ~ 75 DEG C ~ for 24 hours after, cooled and filtered, filtrate is precipitated with toluene, filtering, and filtrate revolving is dry to get drawing
Send out agent TPE-AZO；
The molar ratio of TPE-monoOH and ACVA is 1:4~1:5；The molar ratio of TPE-monoOH and DMAP is 1:2~1:4；TPE-
MonoOH and DCC molar ratios are 1:1~1:2.
（3）The preparation of polymer TPE-monoPNIPAM
By TPE-AZO and monomer NIPAM with 1:100~1:400 molar ratio is dissolved in tetrahydrofuran（THF）In, it is true in 65 ~ 75 DEG C
Sky reaction 20 ~ for 24 hours, it is cooled to room temperature, n-hexane is added to precipitate, filter, purifying is dry to get polymer TPE-monoPNIPAM.
（4）The preparation of TPE-monoPNIPAM-Eu (III) complex
Polymer TPE-monoPNIPAM is dissolved in absolute ethyl alcohol, the dimethyl sulphoxide solution of Europium chloride is added, room temperature is stirred
Reaction 20 ~ for 24 hours is mixed, polymer is settled out with n-hexane, is purified, vacuum drying is matched to get TPE-monoPNIPAM-Eu (III)
Close object --- double fluorescent polymer quanta point materials.
The mass ratio of polymer TPE-monoPNIPAM and Europium chloride is 10:1~10:2.
The synthesis formula of TPE-monoPNIPAM-Eu (III) complex is shown below：
TPE-monoPNIPAM and TPE-monoPNIPAM-Eu (III) complex of above-mentioned preparation1H-NMR is shown in Fig. 1.
Two, the structural characterization of TPE-monoPNIPAM-Eu (III) complex
1, FT-IR spectrograms
Fig. 2 is the FT-IR spectrograms of double fluorescent polymer quantum dot TPE-monoPNIPAM-Eu (III) prepared by the present invention.From
FT-IR spectrograms can be seen that TPE-monoPNIPAM in 3500 ~ 3400cm-1Hydroxyl peak on the phenyl ring at place gradually weaken take and
Instead of be 3400 ~ 3200cm-1Broader amide N-H stretching vibration peaks, 1640 ~ 1600cm-1With 1520 ~ 1500cm-1The benzene at place
Ring carbon skeleton peak still retains, since the stretching vibration of C=O is in 1680 ~ 1630cm-1Place absorbs also stronger；3100~3010cm-1Place's double stretching vibrations built of existing alkene still retain；In the complex of Eu, due to the coordination with Eu (III), phase
More original absorption peak has very big change, in 3100 ~ 3550cm-1The wide peak that becomes at place illustrates that amido bond is sent out in complex
A degree of crosslinking is given birth to, C=O absorption peaks are stronger, this illustrates that Eu mainly affects N the and O elements on amido bond.
3, XPS spectrum map analysis
By the complex TPE-monoPNIPAM-Eu (III) of polymer TPE-monoPNIPAM and Eu respectively to tri- element of C, N, O
XPS tests are carried out.The XPS figures and C1s of the respectively TPE-monoPNIPAMTPE-monoPNIPAM-Eu (III) of Fig. 3,4
（a）、N1s（b）、O1s（c）XPS figure.The Bond energy change that can be seen that front and back N, O element of coordination from XPS analysis collection of illustrative plates is very big,
Their bond energy has a degree of raising in complex, and showing Eu (III) can be coordinated with N, O on PNIPAM
Effect.In europium complex, the content that element is tested out by XPS is listed in Table 1 below.
4, EDS is analyzed
Test element composition and content that EDS further determines material（See Fig. 5 and table 2）, each element content composition with
XPS test results slightly difference.This is because the depth of EDS tests is smaller, the content ratio of material surface is only detected.Knot
Close XPS results, it can be deduced that Eu is preferable to the coordination ability of amido bond in polymer TPE-monoPNIPAM, and can be fine
Coordination on N, O atom.
5, UV-vis is analyzed
In order to further probe into its luminosity, UV-vis is tested.Fig. 6 is the UV-vis of TPE-monoPNIPAM-Eu (III)
Figure.As shown in fig. 6, in complex TPE-monoPNIPAM-Eu (III), the introducing of europium makes complex pair 350 ~ 530nm models
UV Absorption in enclosing is stronger, this is conducive to complex and is inspired red fluorescence, and complex is near ultraviolet and visible light
Absorbability is stronger, range is wider, this illustrate complex can more efficiently be absorbed when receiving burst of ultraviolel excitation can, to
More first energy level ground state electrons are made to transit to more high level, more excitation state electronics give off energy back in the form of light
To ground state, to enhance luminous efficiency.The fluorescence of complex is stimulated the difference of wavelength and different, in 300 ~ 400nm ranges
The interior color that can make complex crossfades into red by blue, and two kinds of colors are not interfere with each other.The material within the scope of 300 ~ 360nm
Material blue-light-emitting account for leading role, show blue light, mainly in conjunction with PNIPAM and TPE characteristic light respectively in 380nm
And 460nm, the two larger peak half-peak breadths are difficult to separate but be in blue light range, so indigo plant is integrally presented in the fluorescence of solution
Color.And blue light strength gradually weakens within the scope of 360 ~ 400nm, red light intensity enhancing, feux rouges finally occupies leading role, shows
The feux rouges gone out is mainly the very high visible peak of two red of excitation purity that the coordination of europium generates, and as 590nm and 614nm's is corresponding
In5D0→7F1, 5D0→7F2Electron transition and the fluorescence discharged.Fluorescence photo under corresponding excitation it is also seen that：
When the monochromatic light of difference excitation passes through solution, blue, red are will present out in solution.So we have selected 365nm and 400nm
Respectively the blue of complex, red fluorescence maximum excitation wavelength.The fluorescence of this polymer quantum dot can be stimulated wave
It grows and is controlled within the scope of 300 ~ 400nm, the complex light of generation is as shown in Figure 7,8 on Standard colour board：Within the scope of 300 ~ 340nm
Mainly PNIPAM and Eu complexs generate blue light and feux rouges respectively, within the scope of 340 ~ 400nm, mainly TPE and Eu cooperations
Object generates blue light and feux rouges respectively, therefore the straight line of two complex lights is showed on Standard colour board.
Aggregation photoluminescence property is not only the material can be presented good fluorescence under solid（See Fig. 9）, also so that thin
Fluorescence is stronger in the state that endocytosis is bitten, and is more advantageous in its open application prospect of field of biology.Work as TPE-monoPNIPAM-Eu
(III) swing space of strand almost spread apart when being dissolved in good solvent absolute ethyl alcohol, the upper phenyl ring of TPE is bigger, works as quilt
When excitation, complex can be fallen thermal dissipation in the form of thermal energy by the vibration of phenyl ring, to the relatively low real estate of the efficiency of light energy utilization
Raw fluorescence；When the volume fraction increase of poor solvent dichloromethane, molecule is promoted to assemble, intermolecular distance is smaller, hinders molecule
The vibration of middle phenyl ring and reduce strand activity space so that molecule cannot be dissipated in the form of thermal energy excitation can, to increase
Fluorescent yield is added.
The AIE performances of TPE-monoPNIPAM-Eu (III) material can promote molecule to be sent out more under cell phagocytosis state
Strong fluorescence, and PNIPAM chains are a kind of polymer of Thermo-sensitive, when temperature is higher, hydrophobic effect increases around PNIPAM chains
By force, deposited phenomenon is shown.Figure 10 is influence of the temperature to the fluorescence of TPE-monoPNIPAM-Eu (III)：Swash at 365nm
When hair, temperature TPE-monoPNIPAM-Eu (III) at 29 DEG C or less shows clear state in aqueous solution（LCST=29
℃）, hydrophilic and hydrophobic phase transformation occurs in 29 ~ 33 DEG C of sections so that solution becomes white emulsion by becoming cloudy clearly after 33 DEG C.This
Fluorescence Increasing when kind accumulation process can also make solution be excited, can make the material generate the change of phase under sendible temperature
Change, to be a kind of good temperature-responsive material.
The feature of polymer quantum dot maximum is that its three-dimensional dimension is in nano-scale range, both has regular quantum
The size of point has the property of polymer again, still test SEM and can intuitively find out its size and shape.Such as Figure 11 institutes
Show, dissolved in absolute ethyl alcohol, then dichloromethane is added dropwise to make molecule slow self assembly in system, it can be seen that two kinds of objects
Matter can be self-assembled into nano-scale spheres shape, and Size Distribution is between 30nm ~ 60nm, so this polymer quantum dot is by success
It is made.
The polymer quantum dot, which can well dye cytoplasm, to be shown to the coloration result of Hela cells, in cytoplasm
Middle aggregation highlights fluorescence to generate, blue and red complex light can be generated under different excitation wavelengths, is especially existed
365nm can generate bright blue light when exciting, and highlighted feux rouges is generated when 395nm is excited（Figure 12）.It can be in Hela cells
Assemble and show highlighted fluorescence in matter, can preferably be applied in biological field, such as cancer cell tracking, drug release.
In conclusion the present invention successfully synthesizes a kind of polymer quantum dot with double fluorescence of good biocompatibility,
Group occurs by the hydrophobic TPE blues with AIE properties and amphiphilic PNIPAM is covalently joined together, it can be certainly
It is assembled into the polymer quantum dot TPE-monoPNIPAM of nano-scale, TPE- is made by the coordination with Eu (III)
MonoPNIPAM-Eu (III), this polymer quantum dot can be self-assembled into the bead of monodispersity, size about 30 ~ 60nm,
Double fluorescent characteristics well are shown simultaneously, and two kinds of colors can be good at independent separate in 365 ~ 400nm excites scopes.This
Outside, which can be changed phase by the control of temperature, and LCST is about 29 DEG C, and transition temperature range is also relatively narrow.
The polymer quantum dot, which can well dye cytoplasm, to be shown to the coloration result of Hela cells, is assembled in cytoplasm, from
And generate and highlight fluorescence, blue and red complex light can be generated under different excitation wavelengths, especially excited in 365nm
When can generate bright blue light, highlighted feux rouges is generated when 395nm is excited, is applied in the double-colored cell imagings of Hela,
It is able to observe that strong blue, red cell imaging, is preferably applied in biological field, such as cancer cell tracking, drug
Release etc..
Description of the drawings
Fig. 1 is TPE-monoPNIPAM and TPE-monoPNIPAM-Eu (III) complex1H-NMR。
Fig. 2 is the FT-IR spectrograms of TPE-monoPNIPAM-Eu (III) complex prepared by the present invention.
The XPS that Fig. 3 is TPE-monoPNIPAMTPE-monoPNIPAM-Eu (III) schemes
C1s, N1s, O1sXP that Fig. 4 is TPE-monoPNIPAMTPE-monoPNIPAM-Eu (III) scheme.
The EDS that Fig. 5 is TPE-monoPNIPAMTPE-monoPNIPAM-Eu (III) schemes.
The UV-vis that Fig. 6 is TPE-monoPNIPAM-Eu (III) schemes.
The fluorescence wavelength that is stimulated that Fig. 7 is TPE-monoPNIPAM-Eu (III) is compound glimmering within the scope of 300 ~ 400nm
Light.
Fig. 8 is position of the complex light of TPE-monoPNIPAM-Eu (III) on Standard colour board.
Fig. 9, which is the aggregation extent of TPE-monoPNIPAM-Eu (III), leads to Fluorescence Increasing（AIE）.
Figure 10 is influence of the temperature to the fluorescence of TPE-monoPNIPAM-Eu (III).
Figure 11 is the scanning electron microscope of the self-assembled nanometer bead of TPE-monoPNIPAM-Eu (III).
Figure 12 is the blue of the Hela cells dyed under the excitation of 365nm and 400nm respectively, red cell picture.
Specific implementation mode
Below by specific embodiment to the preparation of TPE-monoPNIPAM-Eu of the present invention (III), performance and application make into
One step explanation.
1, the preparation of TPE-monoPNIPAM-Eu (III)
（1）The preparation of Europium chloride solution
It weighs the europiumsesquioxide white powder of 1.0mmol and concentrated hydrochloric acid is slowly added dropwise in 50mL beakers, under stirring to not having
Foam generates, and adds to the concentrated hydrochloric acid of 20.0mL, adds the N of 5.0mL, N- dimethyl sulfoxide (DMSO)s, and heating evaporation is to solid at 110 DEG C
It is dissolved into solution no longer to volatilize, solution is flaxen EuCl at this time3Dimethyl sulphoxide solution（A concentration of 0.4 mmol/mL）.
（2）Hydroxyl tetraphenyl ethylene（TPE-monoOH）Preparation
In ice-water bath, three mouthfuls of burnings of 250mL are added in the 4- dihydroxy benaophenonels and 1.0mmol benzophenone of 1.0mmol simultaneously
In bottle, the THF of the Zn powder, 150.0mL that add 2.0mmol vacuumizes environment, keeps system anhydrous and oxygen-free, stir as solvent
The titanium tetrachloride for mixing lower injection 3.0mmol, then is transferred in 75 DEG C of oil bath environment, and 20.0mL, 10% are for 24 hours injected in reaction afterwards
K2CO3Quenching reaction, ethyl acetate extraction are collected, revolving drying, obtain the crude product of brown color, crude product crosses silica gel chromatographic column
（With 1:The petrol ether/ethyl acetate of 1v/v is mobile phase）, first phosphor dot is TPE-monoOH, yield 60%.
（3）The preparation of TPE-monoPNIPAM
1.0mmolTPE-monoOH and 4.0mmolACVA are taken, is dissolved in the THF solution of 50.0mL, 3mmol DMAP are added
And 1mmolDCC, it vacuumizes and keeps anhydrous and oxygen-free environment（Or argon gas protection）, after 75 DEG C of heating reactions for 24 hours, cooled and filtered, filter
Liquid is precipitated with toluene, and filtering, filtrate rotates drying, i.e., TPE-AZO.
TPE-AZO and monomer NIPAM is pressed 1:100 molar ratio is dissolved in the dry THF of 100mL, 75 DEG C of vacuum reactions
For 24 hours, it is cooled to room temperature, adds n-hexane precipitation filtering, filter out polymer, purify vacuum drying at room temperature.As TPE-
MonoPNIPAM, Mn ≈ 18000.
1H-NMR(600M, D2O): δ=4.64(s, 366H), 3.77(s, 41H), 1.94(d, J=69.6Hz,
29H), 1.46(t, J=8.7Hz, 73H), 1.31~1.28(m, 4H), 1.02(s, 247H)。
（4）The preparation of TPE-monoPNIPAM-Eu (III) complex
The polymer TPE-monoPNIPAM for taking 1.0g, is dissolved in 20.0mL absolute ethyl alcohols, reinjects the EuCl that 1mL is prepared3
Solution stirs 20h, polymer is settled out with n-hexane, purifies, and is dried in vacuo to get target product --- TPE-
MonoPNIPAM-Eu (III) complex.
2, to the dyeing of Hela cells
12 hole plate cell plates culture Hela cells for 24 hours, culture substrate be the fetal calf serum containing 1% streptomysin and 10%
1640 solution；In TPE-monoPNIPAM-Eu (III) culture medium containing 100 μ g/mL, humidity be 5%, temperature 37
It after being cultivated one day under conditions of DEG C, isolates cell and is rinsed with phosphate buffer solution, divide under confocal fluorescent microscopic
Blue, red cell picture are not obtained under the excitation of 365nm and 400nm, as shown in figure 12.
Claims (10)
1. a kind of preparation method of double fluorescent polymer quanta point materials, includes the following steps：
（1）The preparation of 4- hydroxyphenyl ethylene：Using tetrahydrofuran as solvent, using zinc powder as reducing agent, TiCl4Catalyst is protected in argon gas
Under shield, 4- dihydroxy benaophenonels and benzophenone are with 1:1~1:2 molar ratio, at 70 ~ 75 DEG C flow back 20 ~ for 24 hours；After answering
It is cooled to room temperature, K is added2CO3Aqueous solution quenching reaction, ethyl acetate extraction, revolving drying, obtains the crude product of brown color；Slightly
Product crosses silica gel chromatograph post separation, and first phosphor dot is 4- hydroxyphenyl ethylene TPE-monoOH；
（2）The preparation of initiator TPE-AZO：4- hydroxyphenyls ethylene and azo -4,4 '-dicyano glutaric acid are dissolved in tetrahydrochysene furan
In muttering, add 4-dimethylaminopyridine and dicyclohexylcarbodiimide, argon gas protection, react 20 in 70 ~ 75 DEG C ~ for 24 hours after, it is cold
But it filters afterwards, filtrate is precipitated with toluene, filtering, and filtrate revolving is dry to get initiator TPE-AZO；
（3）The preparation of polymer TPE-monoPNIPAM：TPE-AZO and monomer NIPAM are dissolved in tetrahydrofuran（THF）In, in
70 ~ 75 DEG C of vacuum reactions 20 ~ for 24 hours, it is cooled to room temperature, n-hexane is added to precipitate, filter, purifying is dry to get polymer TPE-
monoPNIPAM；
（4）The preparation of TPE-monoPNIPAM-Eu (III) complex：Polymer TPE-monoPNIPAM is dissolved in absolute ethyl alcohol
In, the dimethyl sulphoxide solution of Europium chloride is added, reaction 20 ~ for 24 hours is stirred at room temperature, polymer is settled out with n-hexane, is purified,
Vacuum drying is to get TPE-monoPNIPAM-Eu (III) complex --- double fluorescent polymer quanta point materials.
2. a kind of preparation method of double fluorescent polymer quanta point materials as described in claim 1, it is characterised in that：Step（1）
In, the addition of zinc powder be 4- dihydroxy benaophenonels, 0.5 ~ 1.5 times of benzophenone integral molar quantity.
3. a kind of preparation method of double fluorescent polymer quanta point materials as described in claim 1, it is characterised in that：Step（1）
In, TiCl4Addition be 4- dihydroxy benaophenonels, 1.5 ~ 2 times of benzophenone integral molar quantity.
4. a kind of preparation method of double fluorescent polymer quanta point materials as described in claim 1, it is characterised in that：Step（2）
In, the molar ratio of TPE-monoOH and ACVA are 1:4~1:5.
5. a kind of preparation method of double fluorescent polymer quanta point materials as described in claim 1, it is characterised in that：Step（2）
In, the molar ratio of TPE-monoOH and DMAP are 1:2~1:4.
6. a kind of preparation method of double fluorescent polymer quanta point materials as described in claim 1, it is characterised in that：Step（2）
In, TPE-monoOH and DCC molar ratios are 1:1~1:2.
7. a kind of preparation method of double fluorescent polymer quanta point materials as described in claim 1, it is characterised in that：Step（3）
In, the molar ratio of TPE-AZO and monomer NIPAM is 1:100~1:400.
8. a kind of preparation method of double fluorescent polymer quanta point materials as described in claim 1, it is characterised in that：Step（4）
In, the mass ratio of polymer TPE-monoPNIPAM and Europium chloride is 10:1~10:2.
9. double fluorescent polymer quanta point materials prepared by method as described in claim 1, it is characterised in that：It is excited in 365nm
When can generate bright blue light, highlighted feux rouges is generated when 395nm is excited.
10. double applications of the fluorescent polymer quanta point material as cell imaging fluorescer as claimed in claim 9.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109385269A (en) * | 2018-11-08 | 2019-02-26 | 西北师范大学 | A kind of preparation and application of the double fluorescent polymer quantum dots of pH responsive type |
| CN110194822A (en) * | 2019-06-03 | 2019-09-03 | 西北师范大学 | A kind of preparation and application of the double fluorescence Pdots of the temperature sensitive type based on single armed TPE molecule |
| CN110518451A (en) * | 2019-08-09 | 2019-11-29 | 华南理工大学 | The aggregation laser device and preparation method of temperature regulation and photoswitch application |
| CN114854032A (en) * | 2022-05-25 | 2022-08-05 | 西北师范大学 | Preparation and application of water-soluble lanthanide AIE fluorescent nanoparticles |
| CN116496169A (en) * | 2023-06-26 | 2023-07-28 | 天津城建大学 | Amphiphilic tetraphenyl ethylene derivative, fluorescent sensing film, preparation method and application |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109385269A (en) * | 2018-11-08 | 2019-02-26 | 西北师范大学 | A kind of preparation and application of the double fluorescent polymer quantum dots of pH responsive type |
| CN109385269B (en) * | 2018-11-08 | 2021-09-24 | 西北师范大学 | Preparation and application of pH-sensitive dual-fluorescent polymer quantum dot |
| CN110194822A (en) * | 2019-06-03 | 2019-09-03 | 西北师范大学 | A kind of preparation and application of the double fluorescence Pdots of the temperature sensitive type based on single armed TPE molecule |
| CN110194822B (en) * | 2019-06-03 | 2021-06-08 | 西北师范大学 | Preparation and application of temperature-sensitive type dual-fluorescence Pdots based on single-arm TPE molecules |
| CN110518451A (en) * | 2019-08-09 | 2019-11-29 | 华南理工大学 | The aggregation laser device and preparation method of temperature regulation and photoswitch application |
| CN114854032A (en) * | 2022-05-25 | 2022-08-05 | 西北师范大学 | Preparation and application of water-soluble lanthanide AIE fluorescent nanoparticles |
| CN116496169A (en) * | 2023-06-26 | 2023-07-28 | 天津城建大学 | Amphiphilic tetraphenyl ethylene derivative, fluorescent sensing film, preparation method and application |
| CN116496169B (en) * | 2023-06-26 | 2023-08-29 | 天津城建大学 | Amphiphilic tetraphenyl ethylene derivative, fluorescent sensing film, preparation method and application |
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