CN104877665A - Luminescent material having aggregation-induced emission, method of making and application thereof - Google Patents
Luminescent material having aggregation-induced emission, method of making and application thereof Download PDFInfo
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Abstract
The invention discloses a luminescent material having aggregation-induced emission, a method of making and an application thereof. The luminescent material herein has properties of aggregation-induced emission/aggregation-enhanced emission with the maximum absorption wavelength red shift to a visible area so that this type of luminescent material has potential applications in the field of biology. The luminescent material allows the formation of transfer of electric charges in a molecule and exhibits strong polar dependent emission in different solvents. The luminescent material does not emit due to strong dipoalr interaction in a molecule, but emits in a weak-polar environment with a cell. The luminescent material can serve as intracellular lipid droplet and intramicroalgae lipid droplet, and has the advantages of high selectivity, high emission stability and high biological compatibility.
Description
Technical field
The present invention relates to a series of luminous organic material, be specifically related to the solid luminescent material with aggregation-induced emission or luminescence enhancement (AIE/AEE) character.
Background technology
Conventional organic luminescence material is always attended by inevitable phenomenon: assemble and cause cancellation (aggregation-caused quenching, ACQ), traditional fluorescent material is usually containing larger π-electron conjugated structure, and this structure is mainly for generation of fluorescence.Under molecular melting state, the solution of fluorescent material demonstrates hyperfluorescenceZeng Yongminggaoyingguang, but strong solution state, state of aggregation or solid-state time, molecular interaction increases, energy trasfer occurs, and result forms exciplex or excimer, and these all can consume excited energy, thus greatly reduce the possibility of fluorescence radiation, well-known ACQ phenomenon that Here it is.But in modern technologies application, in most cases, fluorescent material needs to be processed into state of aggregation or solid-state, and ACQ problem is inevitable, has developed various chemistry (Chem.Commun., 2008,1501 at present; Chem.Commun., 2008,217.), physics and engineering method and the course of processing (Langmuir, 2006,22,4799; Macromolecules 2003,36,5285) thus reach the object weakening ACQ effect, but these trials only obtain less success, major cause is that the formation of aggregate is an intrinsic procedure in condensed phase, is therefore badly in need of keeping strong luminous material and system under figure is assembled in exploitation.
In calendar year 2001, researchist of the present invention has synthesized 1,1-dimethyl-2,3,4,5-tetraphenyl thiophene coughs up (DMTPS) compound, its state of aggregation plays useful but not destructive effects (Chem.Commun.2001 to fluorescent emission, 1740.), researchist also observes a kind of novel phenomenon and hat is called " focusing induced luminescence " (aggregation-induced emission, AIE): under solution state, light emitting molecule is not induced out strong luminescence by forming aggregate.A series of spiral helicine non-luminescent molecule, as thiophene is coughed up and tetraphenyl ethylene (tetraphenylethene, TPE), induces by forming aggregate and sends strong fluorescence (J.Mater.Chem.2001,11,2974; Chem.Commun.2009,4332; Appl.Phys.Lett.2007,91,011111.), investigators have found a variety of molecule with this characteristic afterwards.In addition, designed and Theoretical Calculation by series of experiments, investigators confirm that internal molecular motion limited (RIM) is the major cause (J.Phys.Chem.B2005,109,10061 that cause AIE effect; J.Am.Chem.Soc.2005,127,6335.).
So far, most of AIE twinklers of preparation can only launch blue light and green glow, but for the application of biology aspect, especially whole animal and deep tissues imaging, more preferably the dye molecule of those longwave transmissions, can not be subject to interference (Chem.Mater., 2012 of the autofluorescence of biological tissue like this, 24,812).Fat wherein in organism drips (lipid droplets, LDs) be not only intracellular energy reservoir, but also be a complexity, movable vigorous, the multi-functional organoid of dynamic change, fat drips can along cytoskeletal motor, and interact with other organoid, in lipid metabolism and storage, film is transported, play an important role in proteolytic degradation and intracellular signaling process, study in addition and also show multiple metabolic trouble, as obesity, fatty liver, cardiovascular disorder and diabetes, the depot diseases of neutral fat etc. are often all along with the exception of lipid storage, the biological study of therefore dripping about fat is subject to people's attention day by day, therefore be badly in need of a kind of can the fluorescent dye of specificity fat drip imaging to realize the further investigation of dripping fat.
Summary of the invention
The object of this invention is to provide a kind of newly there is luminescent material of aggregation-induced emission characteristic and preparation method thereof and the application of selectivity in cell imaging, solving luminescent material of the prior art specificity cannot drip the problem of dyeing to fat.
The technical scheme that technical solution problem of the present invention adopts is: a kind of luminescent material with aggregation-induced emission characteristic, includes the group being selected from following arbitrary structural formula:
In structural formula I and II, respectively at least containing substituting group NR
1r
1 ', NR
2r
2 'and NR
3r
3 'any one, R
1, R
1 ', R
2, R
2 ', R
3and R
3 'be selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl and decyl respectively; In structural formula I, substituting group Z is formyl radical, hydroxymethyl or 4-vinylpridine; In formula II, NR
1r
1 ', NR
2r
2 'and NR
3r
3 'in arbitrary substituted radical can be
in formula II, R is selected from alkyl, X
-for SO
3 -, I
-, Cl
-, Br
-, PF
6 -, ClO
4 -, BF
4 -, BPh
4 -or CH
3phSO
3 -, or R and X
-alkylsulphonic acid base negatively charged ion-C can be merged into
nh
2nsO
3 -, n=3 ~ 5;
Tetraphenyl ethylene unit in structural formula I and II at least comprises one, and is connected by C-C singly-bound, C=C double bond or C ≡ C triple bond.
Have in the luminescent material of aggregation-induced emission characteristic of the present invention, containing NR in structural formula I and II
1r
1 'and NR
2r
2 'group, wherein R
1, R
1 ', R
2and R
2 'be methyl; R and X in formula II
-merge into-C
3h
6sO
3 -.
Present invention also offers above-mentioned luminescent material in the application preparing the fluorescent dye that specific stain fat drips, wherein fat drips for the fat in cell or alginite drips.
Present invention also offers the application in the biological dyestuff that above-mentioned luminescent material drips at preparation specificity fat.
Present invention also offers above-mentioned luminescent material in the application for the preparation of screening with the algae selective agent of high biofuel content.
Present invention also offers above-mentioned luminescent material drips the detection agent of content application at formation determination cell lactones.
Present invention also offers the preparation method of above-mentioned luminescent material, comprise the steps:
S1, in the initiator of formula II I, add anhydrous THF solvent, be cooled to-70 DEG C ~-85 DEG C and keep 10min-20min, butyl lithium solution is instilled gradually, and continues to keep low temperature 1.5h-2.5h, then add DMF solvent, the mixing solutions obtained is returned to room temperature, stir 1.5h-2.5h, use aqueous ammonium chloride solution cancellation reaction, also dry with organic solvent extraction, remove solvent at reduced pressure conditions, obtain the luminescent material that Z group is the structural formula I of formyl radical;
Wherein in formula II I, respectively at least containing substituting group NR
1r
1 ', NR
2r
2 'and NR
3r
3 'any one, R
1, R
1 ', R
2, R
2 ', R
3and R
3 'be selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl and decyl respectively; R
4for Cl, Br or I substituting group;
S2, be that the luminescent material of the structural formula I of formyl radical continues to react with sodium hydride, 4-picoline and DMF by the Z group obtained in step S1, stirred at ambient temperature, slowly add water, and with organic solvent extraction, to obtain Z group after drying be 4-vinylpridine and Z group is the luminescent material of the structural formula I of hydroxymethyl simultaneously;
S3, by the Z group obtained in step S1 be the structural formula I of formyl radical luminescent material and
reaction, and add ethanol and a piperidines heating reflux reaction spends the night, go down to desolventize at lower pressure after being cooled to room temperature, obtain the luminescent material of formula II; Wherein R is selected from alkyl, X
-for SO
3 -, I
-, Cl
-, Br
-, PF
6 -, ClO
4 -, BF
4 -, BPh
4 -or CH
3phSO
3 -, or R and X
-alkylsulphonic acid base negatively charged ion-C can be merged into
nh
2nsO
3 -, n=3 ~ 5.
In the preparation process in accordance with the present invention, in formula II I, NR is contained
1r
1 'and NR
2r
2 'group, wherein R
1, R
1 ', R
2and R
2 'be methyl; In step s3, R and X
--C can be merged into
3h
6sO
3 -.
In the preparation process in accordance with the present invention, also comprise step S4, luminescent material step S1, S2 and S3 prepared, by silica column, utilizes ethanol/dichloromethane or petrol ether/ethyl acetate to carry out gradient elution for elutriant.
It should be noted that, described alkyl can be straight chain type, can be also branched chain type, containing 1-10 carbon atom in chain, preferably containing the alkyl of 2-6 carbon atom.
Implement of the present invention to there is luminescent material of aggregation-induced emission characteristic and preparation method thereof and the application in bio-imaging, there is following beneficial effect: luminescent material of the present invention has the aggregation inducing/enhancing characteristics of luminescence (aggregation-induced/enhanced emission, AIE/AEE), dispersion embodies AIE/AEE characteristic in an aqueous medium; It absorbs red shift to/visible region, and then can improve its application possibility in bio-imaging; The THF/H of 90% is greater than at water-content
2can form nanoparticle in O mixed solvent, this nanoparticle can be absorbed by cell or algae; Due to Intramolecular electron transfer character, demonstrate the polarity dependent form characteristics of luminescence under solution state, due to the existence of dipole effect strong in molecule, molecule itself is not luminous, in vivo, starts luminescence due to the more weak nonpolar environment in local; Can drip as the intracellular fat of specific stain and fluorescent dye that fat in green alga body drips, there is highly selective, high-light-fastness and high-biocompatibility advantage; Responsive and show different luminescences under different pH to pH.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of TPE-TMABr, TPE-TEABr, TPE-TMAAl, TPE-TEAAl, TPE-TMAS, TPE-TEAS, TPE-TMAOH and TPE-TEAOH;
Fig. 2 is that TPE-TMABr, TPE-TEABr, TPE-TMAAl and TPE-TEAAl form the UV-visible ray spectrogram measured in solution, concentration: 10 μMs respectively in pure THF;
Fig. 3 A is that TPE-TMAAl is at different water cut mark (f
w) THF/H
2utilizing emitted light spectrogram in O solvent, wherein concentration is 10 μMs, and excitation wavelength is 410nm;
Fig. 3 B is the relative PL intensity (I/I of TPE-TMAAl
0) and maximum emission peak wavelength and THF/H
2the correlogram of different water cut mark in O, I
0=luminous intensity in pure THF, illustration is TPE-TMAAl (10 μMs) is respectively 0% and 95% THF/H in water content
2the fluorescence photo that the solution ultraviolet formed in O etc. obtain under irradiating;
Fig. 4 A is that TPE-TEAAl is at different moisture content (f
w) THF/H
2pL spectrogram in O solvent, wherein concentration is 10 μMs, and excitation wavelength is 420nm;
Fig. 4 B is the relative PL intensity (I/I of TPE-TEAAl
0) and THF/H
2the correlogram of different moisture content in O, I
0=luminous intensity in pure THF;
Fig. 5 A is the PL spectrogram of TPE-TMAAl in different pH damping fluid, and wherein concentration is 10 μMs, and excitation wavelength is 410nm;
Fig. 5 B is the emission maximum peak intensity of TPE-TMAAl and the correlogram of pH;
Fig. 6 A is the PL spectrogram of TPE-TMAS in different pH damping fluid;
Fig. 6 B is the I/I of TPE-TMAS
0with the correlogram of pH;
Fig. 7 is the cytotoxicity of TPE-TMAAl to LeLa cell and liver LO2 cell being measured different concns by MTT;
Fig. 8 A is the images after HeLa cell and TPE-TMAAl (10 μMs) Dual culture 15min under bright-field;
Fig. 8 B is the images after HeLa cell and TPE-TMAAl (10 μMs) Dual culture 15min under fluorescent microscope under photo-excitation conditions, and excitation wavelength is 330nm-385nm;
Fig. 8 C be imaging after HeLa cell and TPE-TMAAlTMAAl (10 μMs) Dual culture 15min under corresponding bright-field and fluorescence imaging be merged into picture;
Fig. 8 D is the images after HeLa cell and Nile red Nile red (100nm/mL) Dual culture 5min under bright-field;
Fig. 8 E is the images that HeLa cell and Nile red Nile red (100nm/mL) cultivate after 5min under fluorescent microscope under photo-excitation conditions, and excitation wavelength is 460nm-490nm;
Fig. 8 F be imaging after HeLa cell and Nile red Nile red (100nm/mL) cultivate 5min under bright-field and fluorescence imaging be merged into picture;
Fig. 9 A is the abosrption spectrogram of TPE-TMAAl in different solvents, and excitation wavelength is 405nm;
Fig. 9 B is the emmission spectrum of TPE-TMAAl in different solvents, and excitation wavelength is 405nm;
Figure 10 is the particle size analysis figure of TPE-TMAAl (10 μMs) Micelle-like Nano-structure of Two formed in MEM under 25 DEG C of conditions;
Figure 11 is that TPE-TMAAl is at the loss of signal (%) of the intracellular fluorescence intensity of the acid-treated HeLa of oil and the correlogram between sweep time; Wherein illustration is along with scanning times (number ofscans) increases (1-55:1,10,20,50) the fluorescence imaging figure of the HeLa cell that the oil dyeed with TPE-TMAAl (10 μMs) is acid-treated, dyeing time: 15min, excitation wavelength: 405nm, filter: 449nm-520nm, irradiation time: 11.22s/scan;
Figure 12 A is with bright copolymerization Jiao (confocal) image after the match of TPE-TMAAl (10 μMs) to the HeLa cell dyeing 15min that oleic acid (50 μMs) processes;
Figure 12 B is copolymerization Jiao (confocal) image after the HeLa cell dyeing 15min processed oleic acid (50 μMs) with TPE-TMAAl (10 μMs) under photo-excitation conditions; Excitation wavelength 405nm.
Figure 12 C is the merging image of Figure 12 A and 12B;
Figure 13 A is with the TPE-TMAAl of 10 μMs to the fluorescence imaging figure of HeLa cell dyeing 15min, excitation wavelength: 330nm-385nm, scale: 20 μm;
Figure 13 B is with the TPE-TMAAl of 10 μMs to the fluorescence imaging figure of liver LO2 cell dyeing 15min, excitation wavelength: 330nm-385nm, scale: 20 μm;
Figure 14 A is the fluorescence imaging figure of TPE-TMAAl (2.5 μMs) to green alga nanometer body dyeing 10min under the DMSO existence of 10vol% under 40 DEG C of conditions, excitation wavelength: 330nm-385nm;
Figure 14 B is that under 40 DEG C of conditions, TPE-TMAAl (2.5 μMs) exists lower to the fluorescence imaging figure after green alga body dyeing 10min at the DMSO of 20vol%, excitation wavelength: 330nm-385nm;
Figure 15 A is measuring (f containing different after the acidifying of TPE-TMAS excessive hydrochloric acid
hex) hexane ethanol/hexane mixed solvent in utilizing emitted light spectrogram, concentration 10 μMs, excitation wavelength: 395nm;
Figure 15 B is the relative PL intensity (I/I of the TPE-TMAS after acidifying
0) and maximum emission peak wavelength and ethanol/hexane mixed solvent in the correlogram of hexane content, I
0=luminous intensity in straight alcohol;
Figure 16 A is at (the f containing different amount with TPE-TEAS after excessive hydrochloric acid acidifying
hex) hexane ethanol/hexane mixed solvent in utilizing emitted light spectrogram, concentration 10 μMs, excitation wavelength: 395nm;
Figure 16 B is the relative PL intensity (I/I of TPE-TEAS
0) and maximum emission peak wavelength and ethanol/hexane mixed solvent in the correlogram of hexane content, I
0=luminous intensity in straight alcohol;
Figure 17 is with the TPE-TMAS of 10 μMs to the fluorescence imaging figure of HeLa cell dyeing 15min, excitation wavelength: 330nm-385nm;
Figure 18 is with the TPE-TEAS of 10 μMs to the fluorescence imaging figure of HeLa cell dyeing 5.5h, excitation wavelength: 330nm-385nm;
Figure 19 A is the utilizing emitted light spectrogram of TPE-TMAOH in the THF/ water mixed solvent of different content water, concentration 10 μMs, excitation wavelength: 367nm;
Figure 19 B is the relative PL intensity (I/I of TPE-TMAOH
0) with the correlogram of water content in THF/ water mixed solvent, I
0=luminous intensity in pure THF;
Figure 20 is with TPE-TMAOH (10 μMs) to the fluorescence imaging figure after HeLa cell dyeing 30min, excitation wavelength: 330nm-385nm.
Embodiment
Below in conjunction with drawings and Examples, the luminescent material having an aggregation-induced emission characteristic to of the present invention and application thereof and preparation method are described further:
The new concrete preparation process of luminescent material of the present invention is described by following embodiment.It should be noted that the luminescent material prepared is only one or more of luminescent material in the structural formula I-II protected in claim represented by each structural formula below, but the luminescent material that the present invention protects is not limited to this.
The synthetic route that wherein the synthesis preparation process of embodiment 1-3 is shown in Figure 1, number in the figure is see table 1.
Table 1:
Embodiment 1: synthesis TPE-TMAAl and TPE-TEAAl
Structural formula: simultaneously see table 1
(1) TPE-TMABr is synthesized
Chinese chemical name: 4,4'-(2-(4-bromo phenyl)-2-vinylbenzene-1,1-substituting group) two (DMA)
English language Chemical title: 4,4'-(2-(4-bromophenyl)-2-phenylethene-1,1-diyl) bis (N, N-dimethylaniline)
Synthetic method: add 4 in the double-neck flask of drying, 4 '-bis-(dimethylamino) benzophenone 1a (3g, 11.2mmol), 4-bromobenzene ketone (3.78g, 14.5mmol) with zinc powder (4.18g, 64mmol), with nitrogen ventilation at least three times while said mixture is degassed, then the THF solvent 80mL of new distillation is added, above-mentioned reactive system is cooled to-78 DEG C in dry ice-propanone bath, keeps at least 15min, dropwise add TiCl
4(6.11g, 32.3mmol), then continues back flow reaction 8h; After being cooled to room temperature, unnecessary zinc is leached, add wet chemical, and with dichloromethane extraction, by filtrate anhydrous magnesium sulfate drying, revolve and steam except desolventizing, silica column on residue, use petrol ether/ethyl acetate (5:1, v/v) as elutriant, yellow solid product 2.33g is obtained, productive rate 42%.HR-MS (MALDI-TOF): C
30h
29brN
2theoretical value be 496.1514, measured value: 496.1523;
1hNMR (400MHz, CDCl
3) δ 7.23 – 7.17 (m, 2H), 7.14 – 7.05 (m, 3H), 7.05 – 6.99 (m, 2H), 6.94 – 6.91 (m, 1H), 6.91 – 6.83 (m, 5H), 6.51 – 6.40 (m, 4H), 2.90 (s, 12H);
13c NMR (100MHz, CDCl
3) δ 148.14,148.08,144.01,143.54,141.16,134.63,132.45,131.88,131.85,131.74,131.71,131.11,131.01,130.73,129.90,126.90,126.75,124.92,118.50,110.73,110.615,110.53,110.46,39.56.
(2) TPE-TEABr is synthesized
Chinese chemical name: 4,4'-(2-(4-bromo phenyl)-2-vinylbenzene-1,1-substituting group) two (N, N-Diethyl Aniline)
English language Chemical title: 4,4'-(2-(4-bromophenyl)-2-phenylethene-1,1-diyl) bis (N, N-diethylaniline)
Synthetic method: similar to the synthetic method of TPE-TMABr, difference is use 4, two (diethylin) benzophenone 1b (3.63g of 4-, 11.2mmol), 4-bromobenzene ketone (3.78g, 14.5mmol), zinc powder (4.18g, 64mmol) and TiCl
4(6.11g, 32.3mmol) is obtained by reacting product 2.5g, productive rate 40%.HRMS (MALDI-TOF), C
34h
37brN
2theoretical value 552.2140; Measured value 552.2225;
1h NMR (400MHz, CDCl
3) δ 7.22-7.16 (m, 2H), 7.10-7.07 (m, 2H), 7.04 (m, 3H), 6.94-6.88 (m, 2H), 6.87-6.81 (m, 4H), 6.45-6.34 (m, 4H), 3.29 (m, 8H), 1.11 (m, 12H);
13c NMR (100MHz, CDCl
3) δ 145.82,145.74,144.47,144.02,141.62,132.65,132.21,132.16,130.93,130.00,127.00,124.88,110.12,110.00,43.53,12.00.
(3) TPE-TMAAl is synthesized
Chinese chemical name: 4-(two (4-(dimethylamino) the phenyl)-1-phenyl vinyl of 2,2-) phenyl aldehyde
English language Chemical title: 4-(2,2-bis (4-(dimethylamino) phenyl)-1-phenylvinyl) benzaldehyde
Synthetic method: add TPE-TMABr (1.5g in the double-neck flask of 100mL, 3mmol), by nitrogen ventilation, air is removed, anhydrous for 40mL THF solvent is injected in reaction flask, and reaction flask is cooled to-78 DEG C of maintenance 15min in dry ice-propanone bath, then n-BuLi (cyclohexane solution 2M) 1.8mL is dropwise slowly added, and temperature is kept 2h at-78 DEG C, add 2mL dry DMF solvent, mixture obtained above is slowly returned to room temperature, and continue stirring reaction 2h, use aqueous ammonium chloride solution cancellation reaction, with dichloromethane extraction also by dried over mgso, revolve at reduced pressure conditions and steam removing organic solvent, residue is by silicon-dioxide column purification, with sherwood oil and dichloromethane gradient, obtain orange/yellow solid product 0.85g, productive rate 63%.HRMS (MALDI-TOF) C
31h
30n
2o theoretical value 446.2358, measured value 46.2361;
1h NMR (400MHz, CDCl
3) δ 9.88 (s, 1H), 7.60 (d,
2j=6.8Hz, 2H), 7.18 (d,
2j=7.6Hz, 2H), 7.13 – 7.08 (m, 3H), 7.04 – 7.02 (m, 2H), 6.91-6.87 (m, 4H), 6.44 (d,
2j=8.8Hz, 4H), 2.90 (s, 12H);
13c NMR (100MHz, CDCl
3) δ 192.27,152.81,149.48,149.33,144.80,144.04,135.68,133.65,132.96,132.86,132.72,132.37,131.82,131.67,131.60,129.36,128.08,126.16,111.75,111.40,40.50.
(4) TPE-TEAAl is synthesized
Chinese chemical name: 4-(two (4-(diethylin) the phenyl)-1-phenyl vinyl of 2,2-) phenyl aldehyde
English language Chemical title: 4-(2,2-bis (4-(diethylamino) phenyl)-1-phenylvinyl) benzaldehyde
Synthetic method: similar to TPE-TMAAl, difference is to use TPE-TEABr (1.66g, 0.3mmol), and the product obtained is 1.00g, productive rate 60%.MS(EI)502.4；
1H NMR 9.87(s,1H),7.59(d,
2J＝6.8Hz,2H),7.18(d,
2J＝8.0Hz,2H),7.12-7.02(m,5H),6.86(m,4H),6.38(d,
2J＝8.4Hz,4H),3.31-3.26(m,8H),1.13-1.10(t,12H)。
Embodiment 2: synthesis TPE-TMAS and TPE-TEAS
Structural formula: simultaneously see table 1
(1) TPE-TMAS is synthesized
Chinese chemical name: 3-(4-(4-(two (4-(dimethylin) the phenyl)-1-phenyl vinyl of 2,2-) styryl) pyridine-1-base) propane-1-sulfonate
English language Chemical title: 3-(4-(4-(2,2-bis (4-(dimethylamino) phenyl)-1-phenylvinyl) styryl) pyridinium-1-yl) propane-1-sulfonate
Synthetic method: add the TPE-TMAAl (0.5g obtained in the step (3) of embodiment 5 in the reaction mixer of 100mL, 1.1mmol) with 3-(4-picoline-1-base) propane-1-sulfonate (0.265g, 1.21mmol), by degassed for this mixture, take a breath three times with nitrogen simultaneously, then add 20mL dehydrated alcohol and a piperidines, reaction backflow is spent the night; To be cooled to room temperature, go down to desolventize at lower pressure, by residue by silica gel chromatography post, use ethanol/dichloromethane to carry out gradient elution, obtain dark red solid product 0.42g, productive rate 60%.HRMS (MALDI-TOF): C
44h
49n
3o
3s theoretical value C
40h
41n
3o
3s, 643.2869; Measured value 644.2957;
1h NMR (400MHz, d
6-DMSO) δ 8.91 (d,
2j=8.0Hz, 2H), 8.16 (d,
2j=8.0Hz, 2H), 7.90 (d,
2j=16Hz, 1H), 7.49 (d,
2j=8.4Hz, 2H), 7.40 (d,
2j=16.4Hz, 1H), 7.17-7.13 (m, 2H), 7.10-7.07 (m, 1H), 7.03-6.97 (m, 4H), 6.80-6.74 (m, 4H), 6.80-6.74 (m, 4H), 6.49-6.43 (m, 4H), 4.63-4.59 (t, 2H), 3.04-3.02 (m, 12H), 2.44-2.41 (t, 2H), 2.24-2.19 (t, 2H).
(2) TPE-TEAS is synthesized
Chinese chemical name: 3-(4-(4-(two (4-(diethylin) the phenyl)-1-phenyl vinyl of 2,2-) styryl) pyridine-1-base) propane-1-sulfonate
English language Chemical title: 3-(4-(4-(2,2-bis (4-(diethylamino) phenyl)-1-phenylvinyl) styryl) pyridinium-1-yl) propane-1-sulfonate
Synthetic method: similar to the synthetic method of TPE-TMAS, difference is to use the TPE-TEAAl (0.55g that in embodiment 5, step (4) obtains, 1.1mmol) with 3-(4-picoline-1-base) propane-1-sulfonate (0.265g, 1.21mmol) be obtained by reacting intense violet color product 0.46g, productive rate 60%.HRMS (MALDI-TOF): C
44h
49n
3o
3s theoretical value 699.3495; Measured value 700.3579;
1h NMR (400MHz, DMSO) δ 8.91 (d, J=6.8Hz, 2H), 8.16 (d, J=6.8Hz, 2H), 7.90 (d, J=16.4Hz, 1H), 7.49 (d, J=8.3Hz, 2H), 7.40 (d,
2j=16.3Hz, 1H), 7.15 (t, 2H), 7.08 (t, 1H), 6.99 (m, 4H), 6.77 (m, 4H), 6.46 (m, 4H), 4.61 (t, 2H), 3.02 (m, 8H), 2.42 (t, 2H), 2.21 (m, 2H), 1.17 (t, 12H);
13cNMR (100MHz, d
6-DMSO) δ 151.88,147.92,145.60,145.44,144.04,143.48,142.23,140.33,134.14,132.01,131.93,131.24,130.60,129.80,129.61,126.91,126.73,124.64,122.73,120.23,109.60,58.04,46.40,43.13,26.32,11.71,11.63.
Embodiment 3: synthesis TPE-TMAOH, TPE-TMAPy and TPE-TEAOH, TPE-TEAPy
Structural formula: simultaneously see table 1
(1) TPE-TMAPy and TPE-TMAOH is synthesized
TPE-TMAPy Chinese chemical name: 4,4'-(2-phenyl-2-(4-(2-(4-pyridyl) vinyl) phenyl) ethene-1,1-substituting group) two (DMA)
TPE-TMAPy English language Chemical title: 4,4'-(2-phenyl-2-(4-(2-(4-pyridinyl) vinyl) phenyl) ethene-1,1-diyl) bis (N, N-dimethylaniline)
TPE-TMAOH Chinese chemical name: (4-(two (4-(dimethylamino) the phenyl)-1-phenyl vinyl of 2,2-) phenyl) methyl alcohol
TPE-TMAOH English language Chemical title: (4-(2,2-bis (4-(dimethylamino) phenyl)-1-phenylvinyl) phenyl) methanol
Synthetic method: add TPE-TMAAl (0.5g prepared by embodiment 5 step (3) in reaction flask, 1.1mmol) with sodium hydride (0.04g, 1.67mmol), by inflated with nitrogen deoxygenation, inject liquid 4-picoline 0.142mL and DMF 20mL, room temperature for overnight, slowly add water and remove unnecessary sodium hydride, with dichloromethane extraction, dried over mgso, the residue removed after solvent crosses post, carries out gradient elution, obtain principal product TPE-TMAOH and by product TPE-TMAPy by petrol ether/ethyl acetate.Wherein, TPE-TMAOH:HRMS (MALDI-TOF) C
31h
32n
2o theoretical value 448.2515, measured value 448.2516;
1h NMR (400MHz, CDCl
3) δ 7.13 – 7.06 (m, 4H), 7.03 (d,
2j=8.0Hz, 5H), 6.89 – 6.82 (m, 4H), 6.43 – 6.34 (m, 4H), 4.60 (d,
2j=5.9Hz, 2H), 3.28 (m, 12H).TPE-TMAPy:HR-MS (MALDI-TOF) C
37h
35n
3theoretical value 521.2829; Measured value 521.2831;
1h NMR (400MHz, CDCl
3) δ 8.53 (d,
2j=5.7Hz, 2H), 7.31 (d,
2j=5.9Hz, 2H), 7.28 – 7.24 (m, 2H), 7.20 (d,
2j=16.3Hz, 1H), 7.12 (m, 2H), 7.06 (m, 6H), 6.96 – 6.85 (m, 6H), 6.46 (t, 4H), 2.89 (m, 12H);
13c NMR (100MHz, CDCl
3) δ 149.36,148.33,148.25,145.72,144.40,144.37,141.44,135.51,132.68,132.40,131.99,131.96,131.49,131.41,131.00,127.05,125.74,125.06,124.18,120.09,110.75,110.63,39.72.
(2) TPE-TEAPy and TPE-TEAOH is synthesized
TPE-TEAPy Chinese chemical name: 4,4'-(2-phenyl-2-(4-(2-(4-pyridyl) vinyl) phenyl) ethene-1,1-substituting group) two (N, N-Diethyl Aniline)
TPE-TEAPy English language Chemical title: 4,4'-(2-phenyl-2-(4-(2-(4-pyridinyl) vinyl) phenyl) ethane-1,1-diyl) bis (N, N-diethylaniline)
TPE-TEAOH Chinese chemical name: (4-(two (4-(diethylin) the phenyl)-1-phenyl vinyl of 2,2-) phenyl) methyl alcohol
TPE-TEAOH English language Chemical title: (4-(2,2-bis (4-(diethylamino) phenyl)-1-phenylvinyl) phenyl) methanol
Synthetic method: similar to the synthetic method of TPE-TMAPy with TPE-TMAOH, difference is the TPE-TEAAl (0.55g using the step (4) of embodiment 5 to obtain, 1.1mmol) with sodium hydride (0.04g, 1.67mmol), reaction preparation TPE-TEAPy and TPE-TEAOH.Wherein, TPE-TEAOH:MS (EI) 504.4;
1h NMR (400MHz, CDCl
3) δ 7.52 (s, 1H), 7.09 (dd, 4H), 7.04 (d, J=8.0Hz, 5H), 6.90 – 6.82 (m, 4H), 6.43 – 6.35 (m, 4H), 4.60 (d, J=5.8Hz, 2H), 3.28 (m, 8H), 1.11 (m, 12H).Wherein TPE-TEAPy:MS (EI) 577.4;
1h NMR (400MHz, CDCl
3) δ 8.53 (d,
2j=8.0Hz, 2H), 7.31 (d,
2j=8.0Hz, 2H), 7.28 (s, 1H), 7.19 (s, 1H), 7.11-7.05 (m, 8H), 6.93-6.86 (m, 5H), 6.43-6.38 (m, 4H), 3.31-3.25 (m, 8H), 1.13-1.09 (m, 12H);
13c NMR (100MHz, CDCl
3) δ 149.43,146.06,145.83,145.72,144.71,144.35,141.73,134.70,132.72,132.30,132.26,132.23,131.44,131.04,130.37,130.32,126.99,125.70,124.85,124.02,120.07,110.10,110.01,43.53,12.00.
Embodiment 4: to the research of the luminescent material application aspect of the TPE derivative of a series of alkylamino functionalization prepared by embodiment 1-3
As shown in Figure 2; for the TPE derivative that alkylamino replaces; when by lithiumation and formylation, bromo being become formyl group; ultraviolet (UV) absorbs and very large red shift (more than 40nm) occurs; this is owing to forming donor-receiver structure (donor-acceptor structure); alkylamino is strong electron contributing group, and formyl radical is electron accepting group.Donor-receiver structure makes luminescent material, in ultraviolet (UV) absorption spectrum and photoluminescence (PL) spectrum, larger red shift occur.
Although luminescent material TPE-TMAAl is minor structure, the red shift of its maximum absorption band, to visible region, as shown in Fig. 3 A, 3B and 4A and 4B, remains with typical AIE characteristic, and luminous maximum value is close to 600nm, orange-yellow in state of aggregation display.Compared with the ultra-violet absorption spectrum at THF solution, there is large Stokes shift 200nm in luminescent material, can avoid the interference of self-absorption.
As shown in Fig. 5 A, 5B and 6A, 6B, due to alkylamino group, compound (Fig. 1) series prepared in embodiment 1-3 to pH sensitive, under different pH conditions, protonation degree is variable, shows different luminescences due to the change of dipole value in molecule.
Be subject to the inspiration of Nile red (Nile Red) the commercial biological dyestuff with analog structure, probe into the application of such luminescent material in bio-imaging.As shown in Figure 7, by MTT colorimetry, display TPE-TMAAl has higher biocompatibility, when Cervical Cancer HeLa Cells and liver LO2 cell concn reach 100 μMs, add in TPE-TMAAl to substratum with Cervical Cancer HeLa Cells and liver LO2 co-culture of cells 24h after, cause apoptosis hardly.The fabulous biocompatibility that has of display TPE-TMAAl, impels its application in cell imaging of research further.
After the TPE-TMAAl of HeLa cell and 10 μMs cultivates 15min, with phosphate buffered saline buffer, too much dyestuff is rinsed out.As shown in Fig. 8 A, 8B and 8C, TPE-TMAAl can independently enter to Hela cell, and the globular adiponectin at short notice in (the 10-15min time is abundant) specified point light cell drips (LDs).In tenuigenin, be easy to be considered to fat with the spheroplast of obvious bright fluorescence drip (LDs).TPE-TMAAl is lipophilic dye, is easy in hydrophobic LDs inner accumulated.Due to AIE character, in dyeing course, increase the concentration of TPE-TMAAl, can not losing the luminous intensity strengthened in specific situation in LDs.As shown in Fig. 8 D, 8E and 8F, in parallel test, use Nile red (Nile red) as staining agent, Nile red is not only by LDs dyeing (yellow point), also by other intracellular structure as plastosome dyeing (emitting red light), this poor specificity make be difficult to use Nile red as fluorescent dye to distinguish LDs and other organoid, let alone observe the dynamic motion of LDs.
Although orange-colored light (illustration see in Fig. 3 B) is sent out in TPE-TMAAl dispersion in an aqueous medium, but green light of turning blue in LDs region (see Fig. 8 B), this luminescence polar sensitive reason to solution environmental that can be understood as TPE-TMAAl causes.LDs is surrounded by the individual layer of phospholipid, and this phospholipid has the internal structure for holding lipid hydrophobic tail, and therefore the internal polar of LDs is very weak.Because the characteristic of distortion Intramolecular electron transfer (TICT), luminescence will blue shift in compared with the environment of low-pole for TPE-TMAAl.In order to confirm this guess, as illustrated in figures 9a and 9b, detect the emmission spectrum of TPE-TMAAl in the solvent of opposed polarity, along with the enhancing of solvent polarity, UV absorbs and PL emmission spectrum all red shift occurs, especially PL emmission spectrum, luminous about 460nm in n-hexane solvent, and become about 630nm luminous in DMSO solvent, demonstrate fabulous solvent discoloration effect.
In order to confirm that TPE-TMAAl enters intracellular mode, dynamic light scattering method is utilized to measure the particle diameter of Micelle-like Nano-structure of Two.Identical with the condition of HeLa cell imaging, namely in the substratum (MEM) containing 0.1vol%DMSO, the TPE-TMAAl of lipophilic forms nanoparticle, as shown in Figure 10, particle size analysis display median size is 178nm, as shown in figure 11, this nanoparticle to enter in cell and builds up in weakly acidic pH LDs, and the hydrophobicity of LDs and inert environments can make nanoparticle resist the destruction of outside stimulus further.The preferably photostabilization of TPE-TMAAl is mainly owing to the inert atmosphere in the formation of Micelle-like Nano-structure of Two and hydrophobic LDs.
As shown in Figure 12 A, 12B, 12C and 13A, 13B, TPE-TMAAl to HeLa cell and the intracellular LDs dyeing of liver LO2 in 15min, can have highly selective to LDs.
Have studied the dyeing of TPE-TMAAl to LDs in green alga body.Diffuse in green alga body to accelerate TPE-TMAAl, use in substratum containing the TPE-TMAAl of same concentrations but the DMSO solvent of different content, DMSO content is higher, and the time that TPE-TMAAl diffuses in green alga body is shorter.When green alga uses the TPE-TMAAl of 10 μMs of concentration to cultivate 10min under 40 DEG C of conditions in 20%DMSO solvent, blur-free imaging as shown in figs. 14 a-b can be obtained, differentiate fat content by the blue-greenish colour luminescence of staining agent.The diameter in green emitting region reflects the size of LDs, and the whole luminance area of imaging is relevant with the total lipid content in green alga body.The above results shows that it is feasible for using TPE-TMAAl to carry out highly screening the algal kind with high biofuel content.
As shown in Figure 15 A, 15B and 16A and 16B, introduce the TPE group that pyridine propanesulfonic acid salt replaces to alkylamino, molecular memory is in extremely strong dipole effect, very faint ruddiness can only be sent out under solid-state, after hydrochloric acid or trifluoroacetic acid acidifying, dipole declines in molecule, again luminous under solid-state.
Although TPE-TMAS eigen state is not luminous, once enter in HeLa cell, with coming to the same thing of TPE-TMAAl, as shown in figure 17, can optionally arrive LDs position, there is highly selective and two-forty (dyeing time: 15min).
TPE-TEAS eigen state is not luminous, after entering HeLa cell, different from the result of TPE-TMAS, as shown in figure 18, TPE-TEAS needs the time longer (5.5h) to HeLa cell dyeing, dyeing does not have obvious selectivity, and the imaging display TPE-TEAS particle dispersion shown in Figure 18 is in whole tenuigenin.
TPE-TMAOH is at THF/H
2obvious AIE character is shown in O mixed solvent.As illustrated in fig. 19 a and fig. 19b, water content is more than 70vol%, and luminescence becomes and sharply strengthens, and AIE index is up to 120.
TPE-TMAOH is once enter in HeLa cell, with coming to the same thing of TPE-TMAAl, as shown in figure 20, TPE-TMAOH can optionally arrive LDs position in 30min, there is highly selective, another product TPE-TMAPy obtained in synthesis TPE-TMAOH process has highly selective dyeing to LDs too, is expected to the staining agent for the preparation of specific stain LDs.
Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, all these improve or conversion all should belong within the protection domain of claims of the present invention.
Claims (10)
1. there is a luminescent material for aggregation-induced emission characteristic, include the group being selected from following arbitrary structural formula:
In structural formula I and II, respectively at least containing substituting group NR
1r
1 ', NR
2r
2 'and NR
3r
3 'any one, R
1, R
1 ', R
2, R
2 ', R
3and R
3 'be selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl and decyl respectively; In structural formula I, substituting group Z is formyl radical, hydroxymethyl or 4-vinylpridine; In formula II, NR
1r
1 ', NR
2r
2 'and NR
3r
3 'in arbitrary substituted radical can be
in formula II, R is selected from alkyl, X
-for SO
3 -, I
-, Cl
-, Br
-, PF
6 -, ClO
4 -, BF
4 -, BPh
4 -or CH
3phSO
3 -, or R and X
-alkylsulphonic acid base negatively charged ion-C can be merged into
nh
2nsO
3 -, n=3 ~ 5;
Tetraphenyl ethylene unit in structural formula I and II at least comprises one, and is connected by C-C singly-bound, C=C double bond or C ≡ C triple bond.
2. the luminescent material with aggregation-induced emission characteristic according to claim 1, is characterized in that, containing NR in structural formula I and II
1r
1 'and NR
2r
2 'group, wherein R
1, R
1 ', R
2and R
2 'be methyl; R and X in formula II
-merge into-C
3h
6sO
3 -.
3. the arbitrary described luminescent material of claim 1-2 is in the application preparing the fluorescent dye that specific stain fat drips.
4. application according to claim 3, is characterized in that, described fat drips for the fat in cell or alginite drips.
5. the application in the biological dyestuff that drips at preparation specificity fat of the arbitrary described luminescent material of a claim 1-2.
6. the arbitrary described luminescent material of claim 1-2 is in the application for the preparation of screening with the algae selective agent of high biofuel content.
7. the arbitrary described luminescent material of a claim 1-2 drips the application of the detection agent of content at formation determination cell lactones.
8. a preparation method for the arbitrary described luminescent material of claim 1-2, comprises the steps:
S1, in the initiator of formula II I, add anhydrous THF solvent, be cooled to-70 DEG C ~-85 DEG C and keep 10min-20min, butyl lithium solution is instilled gradually, and continues to keep low temperature 1.5h-2.5h, then add DMF solvent, the mixing solutions obtained is returned to room temperature, stir 1.5h-2.5h, use aqueous ammonium chloride solution cancellation reaction, also dry with organic solvent extraction, remove solvent at reduced pressure conditions, obtain the luminescent material that Z group is the structural formula I of formyl radical;
Wherein in formula II I, respectively at least containing substituting group NR
1r
1 ', NR
2r
2 'and NR
3r
3 'any one, R
1, R
1 ', R
2, R
2 ', R
3and R
3 'be selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl and decyl respectively; R
4for Cl, Br or I substituting group;
S2, be that the luminescent material of the structural formula I of formyl radical continues to react in DMF with sodium hydride and 4-picoline by the Z group obtained in step S1, stirred at ambient temperature, slowly add water, and with organic solvent extraction, to obtain Z group after drying be 4-vinylpridine and Z group is the luminescent material of the structural formula I of hydroxymethyl simultaneously;
S3, by the Z group obtained in step S1 be the structural formula I of formyl radical luminescent material and
reaction, and add ethanol and a piperidines heating reflux reaction spends the night, go down to desolventize at lower pressure after being cooled to room temperature, obtain the luminescent material of formula II; Wherein R is selected from alkyl, X
-for SO
3 -, I
-, Cl
-, Br
-, PF
6 -, ClO
4 -, BF
4 -, BPh
4 -or CH
3phSO
3 -, or R and X
-alkylsulphonic acid base negatively charged ion-C can be merged into
nh
2nsO
3 -, n=3 ~ 5.
9. preparation method according to claim 8, is characterized in that, containing NR in formula II I
1r
1 'and NR
2r
2 'group, wherein R
1, R
1 ', R
2and R
2 'be methyl; In step s3, R and X
-merge into-C
3h
6sO
3 -.
10. preparation method according to claim 8, it is characterized in that, also comprise step S4, luminescent material step S1, S2 and S3 prepared, by silica column, utilizes ethanol/dichloromethane or petrol ether/ethyl acetate to carry out gradient elution for elutriant.
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| CN115058126B (en) * | 2022-05-16 | 2023-10-03 | 闽都创新实验室 | Styrene hemicyanine fluorescent dye, preparation method thereof and application thereof in rare earth colorful long afterglow luminescent material |
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| CN104877666B (en) | 2017-03-08 |
| CN104877666A (en) | 2015-09-02 |
| CN104877665B (en) | 2017-01-11 |
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