CN103694996B - Triphenylamine derivative/metal nano composite two-photon fluorescent material with living cell developing function and preparation method thereof - Google Patents
Triphenylamine derivative/metal nano composite two-photon fluorescent material with living cell developing function and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a triphenylamine derivative/metal nano composite two-photon fluorescent material with a living body cell developing function and a preparation method thereof, wherein the triphenylamine derivative/metal nano composite two-photon fluorescent material with the living body cell developing function is characterized in that: is prepared from triphenylamine derivative in metal ion Cd2+In the presence of (a), self-assembling by in-situ induction to obtain a composite two-photon fluorescent material; the triphenylamine derivative and the metal ion Cd in the composite two-photon fluorescent material2+In a molar ratio of 1: 1; the structural formula of the triphenylamine derivative is as follows:
Description
One, technical field
The present invention relates to a kind of two-photon fluorescence material and preparation method thereof, specifically a kind of triphenylamine derivative/metal nano Composite Double photon fluorescence material with living cell developing function and preparation method thereof.
Two, background technology
Organic nanoparticles is the important component part of nano material, it has stable morphological structure, design and synthesis and preparation can be come from molecular level, be easy to realize molecule cut out, and the homogeneity of its size easy to control and particle, make it that there is small-size effect, surface effects and quantum tunneling effect.
Inorganic based organic nanocomposite extensively exists at nature, in vital movement process, play very important effect.Organic/Inorganic Composite Nanomaterials is combined by covalent linkage/non covalent bond by the functional organic material of nanoscale and inorganic component and produced, recombination process, along with the coupling of component property, integration, the effect such as collaborative, can bring the change that the enhancing of character is even brand-new.
It is an effective approach that self-assembling method prepares Organic/Inorganic Composite Nanomaterials.Spontaneous assembling process is from simple to complex ubiquitous, has prepared functional film material and the device such as assembling film, sensor, solar cell, light communication element of functionalization dye film, hybrid structure on this basis.These self-assembled materials have the excellent functions such as conduction, electroluminescent, opto-electronic conversion.By molecular self-assembling formed covalent bonding, to have material that is stable and structure-controllable be very important in biosystem, nowadays it has become the focus of this respect research, it becomes an important technology the most at last, can manufacture the Biofunctional materials that large amount of complex is useful.
In recent years, along with developing rapidly of two-photon fluorescence material, two-photon fluorescence technology has had important breakthrough in application aspect.Because two photon transition has very strong selective exitation, so imaging research can be carried out to some particular matters in biological tissue; Adopt the laser of near infrared or infrared band as light source, greatly can reduce the absorption of biological tissue to exciting light, avoid the interference of tissue autofluorescence, obtain stronger fluorescent.The two photon absorption cross section of biological endogenous molecule is mostly very little, so can realize dark-field imaging, background interference is very little.Simultaneously, excite (near infrared) because two-photon technology uses long wave, there is the features such as excitation energy is low, wavelength is long, penetrance is strong, light injury is little, in the fields such as optoelectronic intagration, biomolecules detection, medical diagnosis and Induced Fluorescence Microscopy, have huge applications potentiality and broad prospect of application.
Along with deep exploitation and the widespread use of nanotechnology, nano material develops rapidly in fields such as cell developing, biomolecules detection and medical diagnosiss as two-photon fluorescence material, and the preparation of metal inducement self-assembly organic nano two-photon fluorescence material and character research become a new study hotspot.
Triphenylamine derivative has structure rigidity, luminous efficiency high, attracts the extensive concern of people always.Potential application prospect is all shown in photic, electroluminescent material, solar cell and biomarker.In recent years, people show larger interest for the triphenylamine derivative with two-photon activity as two-photon sensitized material.
The associated viscera of contriver to the application has done following retrieval:
1, http://scholar.google.com net result for retrieval: (2013/12/18)
2, middle National IP Network result for retrieval: (2013/12/18)
Retrieval mode one:
Section name-----has the triphenylamine derivative-metal nanometer composite material 1 of two-photon cell developing function, all has nothing to do with target compound.
Section name-----triphenylamine derivative-metal nanometer composite material 76, all has nothing to do with target compound.
The preparation 63 of section name-----metal inducement triphenylamine derivative-metal nanometer composite material, all has nothing to do with target compound.
Retrieval mode two:
-----has the triphenylamine derivative-metal nanometer composite material 96 of two-photon cell developing function in full, all has nothing to do with target compound.
The preparation 448 of-----metal inducement triphenylamine derivative-metal nanometer composite material in full, all has nothing to do with target compound.
------triphenylamine derivative-metal nanometer composite material 1822 in full, all has nothing to do with target compound.
Retrieval mode three:
Keyword----there is the triphenylamine derivative-metal nanometer composite material of two-photon cell developing function without pertinent literature.
The preparation of keyword-----metal inducement triphenylamine derivative-metal nanometer composite material is without pertinent literature.
Keyword-----triphenylamine derivative-metal nanometer composite material is without pertinent literature.
Three, summary of the invention
The present invention aims to provide a kind of triphenylamine derivative/metal nano Composite Double photon fluorescence material (being called for short DPASPAN-Cd nano composite material) with living cell developing function and preparation method thereof, technical problem to be solved is: select the suitable organic structure with two-photon absorption and two-photon fluorescence character, and the self-assembly of its nanometer sized materials is induced at metal ion solution situ, optimize the two-photon absorption performance of material, and make it possess hypotoxicity and strong two-photon developing function, thus be suitable for biological applications cell developing.
The present invention there is the triphenylamine derivative (DPASPAN) of two-photon absorption and two-photon fluorescence emission function as organic constituent, at Cd
2+inducing action under, Organic/Inorganic Composite Nanomaterials-DPASPAN-Cd nano composite material is prepared by original position induction self-assembly mode, the DPASPAN-Cd nano composite material of preparation has comparatively high-fluorescence quantum yield, and has the characteristic of lower bio-toxicity and biopsy cell's two-photon absorption fluorography.
The present invention has the triphenylamine derivative/metal nano Composite Double photon fluorescence material of living cell developing function, is in Metal Ions Cd by triphenylamine derivative
2+existence under the Composite Double photon fluorescence material that obtains of original position induction self-assembly;
Triphenylamine derivative and described Metal Ions Cd described in described Composite Double photon fluorescence material
2+mol ratio be 1:1;
The structural formula of described triphenylamine derivative is:
The present invention has the preparation method of the triphenylamine derivative/metal nano Composite Double photon fluorescence material of living cell developing function, operates according to the following steps:
A, by triphenylamine 0.01mol, POCl
320mL and DMF10mL adds in reactor, and in 70 DEG C of stirring reaction 40-60min, reaction terminates rear decompressing and extracting DMF, cool to room temperature, and solid is successively through column chromatography (elutriant is ethyl acetate and the sherwood oil mixing solutions that forms of 1:2 by volume), CH
2cl
2faint yellow intermediate 1 is obtained after recrystallization;
The structural formula of described intermediate 1 is:
B, intermediate 10.01mol to be dissolved in 20mL methyl alcohol, to add NaBH
40.02mol, NaBH
4be divided into three times to add, the interval time at every turn added is 15 minutes, and to reduce the severe degree of reaction, stirring at room temperature reaction 6h, steams and obtain intermediate 2 except after methyl alcohol;
The structural formula of described intermediate 2 is:
C, intermediate 20.01mol and triphenyl phosphorus 0.015mol is dissolved in 30mL chloroform obtains solution A, KI0.01mol is dissolved in 1mL water and obtains solution B, the catalyzer 18-C-6 of Glacial acetic acid 5mL and intermediate 2 quality 5% will be added after solution A and solution B mixing, stirring at room temperature reacts seven days, it is complete that TLC tracks to raw material reaction, is spin-dried for chloroform, poured in p-Xylol by the reaction mixture of remainder and wash away triphenyl phosphorus, collect the solid of separating out, after drying, obtain intermediate 3;
The structural formula of described intermediate 3 is:
D, intermediate 30.01mol is dissolved in 10mLDMF the DMF solution obtaining intermediate 3, terephthalaldehyde 0.01mol is dissolved in 5mLDMF the DMF solution obtaining terephthalaldehyde, the DMF solution of the DMF solution of described intermediate 3 and described terephthalaldehyde is mixed, stirring at room temperature reaction 8-12 hour, TLC follows the tracks of, and after reaction terminates, reaction mixture is dissolved in 500mLCH
2cl
2in, 150mL washes four times, anhydrous MgSO
4drying, revolves and steams except desolventizing, then obtains yellow intermediate 4 after column chromatography (elutriant is sherwood oil and the ethyl acetate mixing solutions that forms of 50:1 by volume);
The structural formula of described intermediate 4 is:
E, to be dissolved in 30mL acetonitrile by intermediate 41mmol, to add 4 hexahydropyridines, return stirring reaction 8-12 hour, TLC follow the tracks of, and after reaction terminates, reaction mixture are dissolved in 500mLCH
2cl
2in, 100mL washes four times, anhydrous MgSO
4drying, revolves and steams except desolventizing, then through column chromatography (elutriant is sherwood oil and the ethyl acetate mixing solutions that forms of 50:1 by volume), obtains yellow DPASPAN;
F, DPASPAN is dissolved in preparation in ethanol and obtains the DPASPAN-ethanolic soln of concentration 0.05mol/L, by 0.01mmolCd (NO
3)
24H
2o is dissolved in preparation in 5mL high purity water and obtains Cd
2+the aqueous solution, pipette 200 μ LDPASPAN-ethanolic solns and add described Cd
2+the aqueous solution in, stir 10 minutes, leave standstill 12 hours, centrifuging, washing and vacuum-drying after obtain target product DPASPAN-Cd.
The present invention take triphenylamine as starting raw material, first prepare intermediate 1---triphenylamine list aldehyde, then intermediate 2 is prepared by intermediate 1---triphenylamine alcohol, subsequently by intermediate 2 and triphenyl phosphorus Reactive Synthesis intermediate 3, intermediate 4 is prepared again by intermediate 3 and terephthaldehyde's aldehyde reaction, triphenylamine derivative DPASPAN is prepared again, finally in cadmium nitrate solution, with Cd by intermediate 4
2+the self-assembly of original position induction DPASPAN-Cd nano composite structure, obtains DPASPAN-Cd nano composite material.
The present invention is to have trianilino group compared with high reaction activity and good biocompatibility as main body, succinctly prepare triphenylamine derivative DPASPAN efficiently, then under the induction of metal ion original position, self-assembly forms DPASPAN-Cd nano composite material, this nano composite material has stronger two-photon absorption and two-photon fluorescence is active, and the present invention has carried out the research of two-photon cell developing to it.
Find through experiment, DPASPAN-Cd nano composite material prepared by the present invention has certain two-photon absorption character between 680nm to 900nm, DPASPAN-Cd nano composite material has very strong single photon fluorescence to launch at 564nm place, have very strong two-photon absorption performance at 840nm place.After HepG2 cell is dyeed by target product, clearly can observe this DPASPAN-Cd nano composite material, to HepG2 nucleus, there is high recognition capability.The discovery of this result of study, for metal ion induction organic/design of metal nano Composite Double multiphoton absorption material, preparation, self-assembly and life science be significant.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the DPASPAN-Cd nano composite material of the present invention's synthesis is the two-photon fluorescence material that a class has cell developing function.There is the features such as excitation energy is low, wavelength is long, penetrance is strong, light injury is little, low toxicity compared with other material, therefore, to cell not damaged, can be used for active somatic cell and detect, there is obvious using value;
2, after HepG2 cell is dyeed by target product, clearly can observe this composite nano materials, to nucleus, there is high recognition capability;
3, raw material is easy to get, and cost is low, and synthesis step is simple, and some experimental procedure is carried out in room temperature, energy-saving and emission-reduction, easy handling.
Four, accompanying drawing explanation
Fig. 1 is syntheti c route figure of the present invention.
Fig. 2 is the SEM style of DPASPAN-Cd nano composite material of the present invention.Can find out at Cd from SEM diffraction pattern
2+under ion induction, DPASPAN is nanofibre-like structure, and be about tens of to nearly hundred microns, wide about 100-500nm, DPASPAN nanofiber is latticed being staggered, very neatly.
Fig. 3 is single photon fluorescence transmitting figure and the two-photon absorption figure (excitation energy is 36mW) of DPASPAN-Cd nano composite material of the present invention.As can be seen from Figure 3, matrix material launches very strong single photon fluorescence at 564nm place, has very strong two-photon absorption at 840nm place.
Fig. 4 be DPASPAN-Cd nano composite material to HepG2 cell fluorescence confocal microscopic image: the burnt Photomicrograph of the single photon fluorescence copolymerization of the HepG2 cell that (a) target product is painted; The burnt Photomicrograph of two-photon fluorescence copolymerization of b HepG2 cell that () target product is painted; (c) light field action diagram; D photo that () is superimposed.
Can be clear that from Fig. 4, target product through the cytolemma of HepG2 cell, enters tenuigenin, and painted completely uniformly to it, and tenuigenin is very high to the uptake ratio of target product, illustrates that target product has very high recognition capability to HepG2 tenuigenin.The preparation of this matrix material for the selecting of cell developing material, prepare, the aspect such as life science, Materials science all had great significance.
Five, embodiment
1, the preparation of intermediate 1
By 2.45g triphenylamine (0.01mol), 20mLPOCl
3100mL round-bottomed flask is placed in, 70 DEG C of stirring reaction 50min, decompressing and extracting DMF, cool to room temperature, the solid ethyl acetate of volume ratio 1:2 and sherwood oil mixed solvent column chromatography, column chromatography product CH with 10mLDMF
2cl
2recrystallization, obtains faint yellow intermediate 1.
1HNMR(400MHz,CDCl
3):δ(ppm)9.84(s,1H);7.71(d,2H);7.39～7.34(m,4H);7.21～7.17(m,6H);7.06(d,2H)。
2, the preparation of intermediate 2
2.75g intermediate 1 (0.01mol) is dissolved in 20mL methyl alcohol, adds NaBH
40.76g (0.02mol), for reducing the violent degree of reaction, NaBH
4be divided into three times to add, the interval time at every turn added is 15 minutes, stirring at room temperature reaction 6h, and reaction terminates rear steaming except methyl alcohol and obtains intermediate 2.
1HNMR(400MHz,CDCl
3)：δ(ppm)7.29(t,4H,J=7.2Hz);7.02(t,8H,J=6.8Hz)；4.59(s,2H)；
3, the preparation of intermediate 3
2.75g intermediate 2 (0.01mol) and 3.9g triphenyl phosphorus (0.015mol) are dissolved in 30mL chloroform and obtain solution A, another being dissolved in 1mL water by 1.70gKI (0.01mol) obtains solution B, the catalyzer 18-C-6 of 5mL Glacial acetic acid and intermediate 2 quality 5% will be added after solution A and solution B mixing, stirring reaction one week under room temperature condition, TLC tracks to intermediate 2 and reacts completely, revolve and steam removing chloroform, the reaction mixture of remainder is poured in p-Xylol and washes away triphenyl phosphorus, collect the solid of separating out, after drying, obtain intermediate 3;
4, the preparation of intermediate 4
6.5g intermediate 3 (0.01mol) is dissolved in 10mLDMF the DMF solution obtaining intermediate 3, separately 1.35g terephthalaldehyde (0.01mol) is dissolved in 5mLDMF the DMF solution obtaining terephthalaldehyde, the DMF solution of the DMF solution of described intermediate 3 and described terephthalaldehyde is mixed, stirring reaction 10 hours, TLC tracks to and reacts completely, and after reaction terminates, reaction mixture is dissolved in 500mLCH
2cl
2in, 150mL washes four times, anhydrous MgSO
4drying, revolves and steams except desolventizing, then through the sherwood oil of volume ratio 50:1 and ethyl acetate mixed solvent column chromatography, obtains yellow intermediate 4.
1HNMR(400MHz,CDCl
3)：δ(ppm)9.97(s,1H);7.89(d,2H,J=8.0Hz)；7.78(d,2H,J=8.0Hz)；7.57(d,6H,J=8.8Hz)；7.45～7.41(d,1H,J=16.4Hz)；7.34(t,4H,J=7.6Hz)；7.24～7.20(d,1H,J=16.4Hz)；6.96(d,2H,J=8.4Hz)；
5, the preparation of triphenylamine derivative (DPASPAN)
Be dissolved in 30mL acetonitrile by 0.38g intermediate 4 (1mmol), add 4 hexahydropyridines, return stirring reacts 10 hours, and TLC follows the tracks of, and after reaction terminates, reaction mixture is dissolved in 500mLCH
2cl
2in, 100mL washes four times, anhydrous MgSO
4drying, revolves and steams except desolventizing, then through the sherwood oil of volume ratio 50:1 and ethyl acetate mixed solvent column chromatography, obtains yellow DPASPAN.
1HNMR(400MHz,CDCl
3)δ(ppm):7.64(m,5H);7.53(d,2H,J=8.0Hz);7.35(s,1H);7.33(s,2H);7.32(d,2H,J=7.6Hz);7.14(d,1H,J=16.4Hz);7.09(t,4H,J=8.4Hz);7.02(d,2H,J=8.4Hz);6.96(d,2H,J=8.4Hz);6.45(d,1H,J=16.8Hz)。
6, the preparation of target product DPASPAN-Cd nano composite material
DPASPAN is dissolved in preparation in ethanol and obtains the DPASPAN-ethanolic soln of concentration 0.05mol/L, by 3.10mgCd (NO
3)
24H
2o (0.01mmol) is dissolved in preparation in 5mL high purity water and obtains Cd
2+the aqueous solution, pipette 200 μ LDPASPAN-ethanolic solns and add described Cd
2+the aqueous solution in, stirring at room temperature 10 minutes, leave standstill 12 hours, centrifuging, washing and vacuum-drying after obtain target product DPASPAN-Cd nano composite material.
The structure SEM of DPASPAN-Cd nano composite material characterizes, and sees Fig. 2.
Single photon fluorescence and the two-photon absorption character of DPASPAN-Cd nano composite material the results are shown in Figure 3.
7, DPASPAN-Cd nano composite material two-photon cell developing effect
To clean up and 6 hole tissue culturing plates put into by the cover glass of sterilizing, liver cancer tissue cell (HepG2 cell) 5 × 10
5the density in individual/hole is seeded in the 6 orifice plate culture dish of diameter 35mm, and carry out cell cultures with DMEM as cell culture medium, containing foetal calf serum (10%), penicillin (100 μ g/mL) and Streptomycin sulphate (100ug/mL) in cell culture medium.Tissue Culture Dish is placed in containing 5%CO
2and 95%O
2incubator in holding temperature 37 DEG C carry out cell cultures 24h, with PBS (phosphoric acid buffer, pH=7.4, Gibco Reagent Company produce) washing HepG2 cell three times, wash away substratum.Then the DMSO solution (20 μMs) of 4 μ LDPASPAN-Cd is added respectively, cultivate 24h, with 4 DEG C of PBS buffered soln (pH=7.4) flush cover slides 6 ~ 7 times, drip 1mL4% paraformaldehyde/PBS solution fixed cell 10min, distilled water flushing cover glass 6 ~ 7 times.Cover glass is stuck in clean glass slide, is placed in observation of cell form and fluorescence picked-up situation under laser confocal microscope (LSM-710, Zeiss, Germany), the results are shown in Figure 4.
Can be clear that from Fig. 4, target product through the cytolemma of HepG2 cell, enters tenuigenin, and painted completely uniformly to it, intercellular substance is very high to the uptake ratio of nano material, illustrates that target product has very high recognition capability to HepG2 intercellular substance.The preparation of this matrix material for the selecting of cell developing material, prepare, the aspect such as life science, Materials science all had great significance.
Claims (1)
1. there is a preparation method for the triphenylamine derivative/metal nano Composite Double photon fluorescence material of living cell developing function, it is characterized in that operating according to the following steps:
A, by triphenylamine 0.01mol, POCl
320mL and DMF10mL adds in reactor, and in 70 DEG C of stirring reaction 40-60min, reaction terminates rear decompressing and extracting DMF, cool to room temperature, and solid is successively through column chromatography for separation, CH
2cl
2faint yellow intermediate 1 is obtained after recrystallization;
The structural formula of described intermediate 1 is:
B, intermediate 10.01mol is dissolved in methyl alcohol, adds NaBH
40.02mol, stirring at room temperature reaction 6h, steams and obtains intermediate 2 except after methyl alcohol; NaBH in step b
4be divided into three times to add, the interval time at every turn added is 15min;
The structural formula of described intermediate 2 is:
C, intermediate 20.01mol and triphenyl phosphorus 0.015mol is dissolved in chloroform obtains solution A, solution B is obtained by soluble in water for KI0.01mol, the catalyzer 18-C-6 of 5% of Glacial acetic acid 5mL and intermediate 2 quality will be added after solution A and solution B mixing, stirring at room temperature reacts seven days, chloroform is spin-dried for after reaction terminates, the reaction mixture of remainder is poured in p-Xylol and washes away triphenyl phosphorus, collect the solid of separating out, after drying, obtain intermediate 3;
The structural formula of described intermediate 3 is:
D, intermediate 30.01mol is dissolved in DMF the DMF solution obtaining intermediate 3, terephthalaldehyde 0.01mol is dissolved in DMF the DMF solution obtaining terephthalaldehyde, the DMF solution of the DMF solution of described intermediate 3 and described terephthalaldehyde is mixed, stirring at room temperature reaction 8-12 hour, is dissolved in 500mLCH by reaction mixture after reaction terminates
2cl
2in, successively through washing, anhydrous MgSO
4dry, revolve to steam and obtain yellow intermediate 4 except after desolventizing and column chromatography for separation;
The structural formula of described intermediate 4 is:
E, be dissolved in acetonitrile by intermediate 41mmol, add 4 hexahydropyridines, return stirring reaction 8-12 hour, TLC follow the tracks of, and after reaction terminates, reaction mixture are dissolved in 500mLCH
2cl
2in, successively through washing, anhydrous MgSO
4dry, revolve to steam and obtain yellow DPASPAN except after desolventizing and column chromatography for separation; The structural formula of described DPASPAN is:
F, DPASPAN is dissolved in preparation in ethanol and obtains the DPASPAN-ethanolic soln of concentration 0.05mol/L, by 0.01mmolCd (NO
3)
24H
2o is dissolved in preparation in 5mL high purity water and obtains Cd
2+the aqueous solution, pipette 200 μ LDPASPAN-ethanolic solns and add described Cd
2+the aqueous solution in, stir 10 minutes, leave standstill 12 hours, centrifuging, washing and vacuum-drying after obtain target product DPASPAN-Cd; DPASPAN and Cd in target product DPASPAN-Cd
2+mol ratio be 1:1.
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