CN104673275A - An activated luminescence material and a method for preparing the same - Google Patents

An activated luminescence material and a method for preparing the same Download PDF

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CN104673275A
CN104673275A CN201410539977.0A CN201410539977A CN104673275A CN 104673275 A CN104673275 A CN 104673275A CN 201410539977 A CN201410539977 A CN 201410539977A CN 104673275 A CN104673275 A CN 104673275A
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tpe
luminescent material
pcl
activation
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CN104673275B (en
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唐本忠
梁国栋
秦玮
林荣业
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HKUST Shenzhen Research Institute
Hong Kong University of Science and Technology HKUST
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HKUST Shenzhen Research Institute
Hong Kong University of Science and Technology HKUST
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Abstract

The invention relates to the technical field of fluorescent material, specifically to an activated luminescence material and a method for preparing the same. Different biomolecules are combined to tetraphenyl ethylene through condensation reaction, so the biocompatible activated luminescence material having AIE/AEE features can be obtained. The biomolecules contain water soluble activated luminescence molecules with high fluorescent quantum yield, which have excellent biocompatibility in a solution state and a solid state, and crystalline polymer which can form nanosheets in a water-soluble medium. The obtained activated luminescence material can be applied to living cell fluorescence staining, sensitive explosive detecting and the like.

Description

A kind of activation luminescent material and preparation method thereof
Technical field
The present invention relates to fluorescent material technical field, especially relate to a kind of activation luminescent material and preparation method thereof.
Background technology
Luminous organic material is applied widely because of it and is more and more received publicity, and luminous organic material is mainly used in bio-imaging (Chem.Sci., 2012,3,984), electronic technology (Adv.Mater., 2011,23,926-952 at present; Chem.Sci., 2011,2,2402; Chem.Rev.2007,107,1011), optical technology (Adv.Master., 2012,24,1703-1708) with storage media (Adv.Master., 2012,24, the field such as 1255-1261), but due to energy trasfer and the formation of excimer (excimers) and exciplex (exciplexes) and the phenomenon of the gathering fluorescent quenching (aggregation-caused quenching, ACQ) caused, cause the luminescence when solid state of traditional plane dyestuff weak, these seriously can limit the application of plane dyestuff at engineering.
Calendar year 2001, some inventors have found a kind of novel activation light emitting molecule, this molecular aggregates has a positive effect instead of destruction to luminescence process, is therefore called " aggregation-induced emission " (aggregation-induced emission, AIE) molecule.AIE molecule is luminous weak in solution state, and can Net long wave radiation luminescence (Chem.Commun.2001,1740, J.Mater.Chem.2001 in state of aggregation, 11,2974, Chem.Commun.2009,4332, Appl.Phys.Lett.2007,91,011111.).The mechanism that existing people proposes internal molecular motion restriction (restriction of intramolecular motions, RIM) explains AIE phenomenon, by internal molecular motion active in solution state, the energy of excitability electronics is buried in oblivion; And activate RIM process by space inward nature during state of aggregation, produce the excitability electronics (J.Phys.Chem.B2005,109,10061, J.Am.Chem.Soc.2005,127,6335) of a large amount of attenuation.
AIE activates luminescence and utilizes accumulation process to activate luminescence, opens a kind of for creating the new paragon obtaining the luminescent material used with solid-state or state of aggregation.Up to the present, based on the RIM mechanism a large amount of AIE dyestuff of extensive exploitation in the widespread use of a lot of fields, as Organic Light Emitting Diode (OLEDs) (J.Mater.Chem., 2011,21,7210-7216; J.Mater.Chem., 2012,22,11018-11021), chemical sensor (J.Am.Chem.Soc., 2010,132,13951-13953; J.Am.Chem.Soc., 2011,133, the field such as 18775-18784), but not yet have AIE dyestuff about the biocompatibility had for the report in cell imaging, this may be (the Adv.Mater. because the complicacy of viable cell causes, 2011,23,3298-3202; J.Am.Chem.Soc., 2012,134,9569-9572).In fact, the knowledge about AIE dyestuff general character useful in cell imaging also lacks very much, therefore expands its application at bioengineering field in the urgent need to developing the AIE dyestuff of biocompatibility.
On the other hand, explosive detection rises most important in the strick precaution attack of terrorism, in recent years, the attack of terrorism based on explosive substance is becoming increasingly rampant, it is main because explosive substance is easily prepared and can cause extensive injures and deaths, the detection of explosive substance faces lot of challenges, as explosive substance steam forces down the frequent introducing etc. with new explosive composition.Explosive detection comprises collection and confinement of gases and analyzes two steps, at present by mass spectrum and ion mobility spectrometry analyzing and testing explosive substance, but these equipment manufacturing cost are expensive, bulky and operate consuming time, on-line checkingi can not be realized, therefore develop cheap and easy to get, high-sensitivity detecting method is significant to preventing the attack of terrorism, not yet have at present about utilizing AIE to activate luminescent material for the relevant report of detection of explosives.
Summary of the invention
The object of this invention is to provide a kind of activation luminescent material and preparation method thereof, solve in prior art and activate luminescent material for cell imaging and the problem for detection of explosives in the urgent need to the AIE of biocompatibility.
The technical scheme that technical solution problem of the present invention adopts is: a kind of activation luminescent material, and its structural formula is as follows:
Wherein, R 1group is cyclodextrin or poly-epsilon-caprolactone, and described poly-epsilon-caprolactone has 28-156 repeating unit; R 2, R 3and R 4group is selected from C respectively nh 2n+1, C 10h 7, C 12h 9, OC 6h 5, OC 10h 7, OC 12h 9, C nh 2nnCS, C nh 2nn 3, C nh 2nnH 2, C nh 2ncl, C nh 2nbr, C nh 2ni, wherein n=0 ~ 20.
In activation luminescent material of the present invention, described R 1group is cyclodextrin, and described activation luminescent material can be used for the fluorescent visual agent preparing stain living cells.
In activation luminescent material of the present invention, described R 1group is poly-epsilon-caprolactone, and described activation luminescent material can be used for detection of explosives.
The present invention also provides a kind of preparation method activating luminescent material, comprises the following steps:
A, in nitrogen environment, under cold condition, by R 1the compound of group, tetraphenyl ethylene-CO 2h (TPE-CO 2h) and N, N-dicyclohexylcarbodiimide be dissolved in anhydrous dimethyl formamide; It should be noted that it can is by R 1the compound of group, tetraphenyl ethylene-CO 2h (TPE-CO 2h) and N, N-dicyclohexylcarbodiimide be added in anhydrous dimethyl formamide simultaneously and dissolve; Also can be first by R 1the compound of group, tetraphenyl ethylene-CO 2h (TPE-CO 2h) be dissolved in anhydrous dimethyl formamide, then add N, N-dicyclohexylcarbodiimide is dissolved; Also can be R 1the compound of group and tetraphenyl ethylene-CO 2h (TPE-CO 2h) be dissolved in anhydrous dimethyl formamide, N, N-dicyclohexylcarbodiimide is dissolved in anhydrous dimethyl formamide, both solution is mixed again;
B, in nitrogen environment, warm temperature is to stirring reaction under room temperature condition until reacted;
C, filtration, be dropwise added in a large amount of ether by the filtrate obtained under the condition of vigorous stirring, separates out solids;
D, again filtering separation obtain this solids, are dried under vacuum by this solids, obtain activating luminescent material.
In the preparation method of activation luminescent material of the present invention, in step, described R 1the compound of group is cyclodextrin, described cyclodextrin, tetraphenyl ethylene-CO 2h (TPE-CO 2h) and the mol ratio of N, N-dicyclohexylcarbodiimide be 1:1:1, the molecular volume of described cyclodextrin in anhydrous dimethyl formamide is than being 1:30, i.e. 1mol:30L.
In the preparation method of activation luminescent material of the present invention, in step, described R 1group compound is poly-epsilon-caprolactone, described poly-epsilon-caprolactone, tetraphenyl ethylene-CO 2h (TPE-CO 2h) and the mol ratio of N, N-dicyclohexylcarbodiimide be 1:8:2, the molecular volume of described poly-epsilon-caprolactone in anhydrous dimethyl formamide is than being 1:150, i.e. 1mol:150L.
In the preparation method of activation luminescent material of the present invention, in step, described cold condition is 0 DEG C.
In the preparation method of activation luminescent material of the present invention, in stepb, in nitrogen environment, warm temperature was to stirring reaction under room temperature condition 3 days.
In the preparation method of activation luminescent material of the present invention, in step D, bake out temperature is 40 DEG C.
Implement activation luminescent material of the present invention and preparation method thereof, there is following beneficial effect: in the structure of activation luminescent material of the present invention by condensation reaction on tetraphenyl ethylene (TPE) in conjunction with different biological molecules, obtain the biocompatible activation luminescent material with AIE/AEE (aggregation-induced/enhanced emission) characteristic, these biomolecules when being included in solution state and solid state, there is splendid biocompatibility and can be water-soluble the activation light emitting molecule of high-fluorescence quantum yield, and the crystalline polymer of Nano lamellite can be formed in water-soluble medium, the activation luminescent material prepared may be used for the aspects such as live cell fluorescent dyeing and sensitive detection explosive substance.
Accompanying drawing explanation
Fig. 1 is that TPE-β-CD is at DMSO-d 6in 2D ROESY NMR collection of illustrative plates, TPE-β-CD concentration: 2mM;
Fig. 2 is that TPE-α-CD is at DMSO-d 6in 2D ROESY NMR collection of illustrative plates, TPE-β-CD concentration: 2mM;
Fig. 3 is that TPE-γ-CD is at DMSO-d 6in 2D ROESY NMR collection of illustrative plates, TPE-β-CD concentration: 2mM;
Fig. 4 A is with the optimization chemical structure of TPE-CDs under rod pattern, in order to clearly, uses methyl to represent cyclodextrin;
Fig. 4 B is with the optimization chemical structure of TPE-CDs under spatial fit pattern, in order to clearly, uses methyl to represent cyclodextrin:
Fig. 5 is that TPE is absorbed in into the structural representation in CD chamber;
Fig. 6 be TPE-β-CD respectively with 2mM and 40mM concentration at DMSO-d 6in 1h NMR contrasts collection of illustrative plates;
Fig. 7 is that TPE-β-CD is at DMSO-d 6in and do not add adamantine and add the adamantine of 2 equimolar amounts 1h NMR contrasts collection of illustrative plates, TPE-β-CD concentration 40mM;
Fig. 8 be TPE-α-CD respectively with 2mM and 40mM concentration at DMSO-d 6in 1h NMR contrasts collection of illustrative plates;
Fig. 9 be TPE-γ-CD respectively with 2mM and 40mM concentration at DMSO-d 6in 1h NMR contrasts collection of illustrative plates;
Figure 10 is the UV, visible light spectrophotometric collection of illustrative plates of TPE-CDs, TPE-C2 and β-CD respectively in DMSO, and its concentration is 0.1mM;
Figure 11 is the circular dichroism spectrum of TPE-CDs in DMSO, and concentration is 1mM;
Figure 12 A is TPE-CDs, TPE and TPE/CD mixture (mol ratio the is 1:1) fluorescence Spectra respectively in DMSO, and concentration is 5mM;
Figure 12 B is TPE-CDs, TPE and TPE/CD mixture (mol ratio the is 1:1) quantum yield respectively in DMSO, and inserting TPE-CDs, TPE and TPE/CD mixture (mol ratio the is 1:1) fluorescence photo respectively in DMSO under uv irradiating, concentration is 5mM;
Figure 13 is the standard emission spectrum of TPE-CDs, TPE and TPE/CD mixture in DMSO, and concentration is 5mM;
Figure 14 is the time resolved fluorescence spectrum of TPE-CDs and TPE in DMSO;
Figure 15 A is that the bright field of the HeLa cell that TPE-β-CD cultivates observes photo;
Figure 15 B is the fluorescent images of the HeLa cell that TPE-β-CD cultivates;
Figure 16 is the DSC collection of illustrative plates of PCL and PCL3k-TPE in cooling scanning and heat scan process, and heating and cooling speed is 10 DEG C/min;
Figure 17 A is the DSC collection of illustrative plates of PCL-TPE in cooling scanning process;
Figure 17 B is the DSC collection of illustrative plates of PCL-TPE in heat scan process;
Figure 18 A is the PL collection of illustrative plates of PCL-TPE in the THF/ water mixed solvent of different water-content;
Figure 18 B is PCL-TPE change curve along with its fluorescence intensity of difference of water content in THF/ water mixed solvent, and radiation wavelength is 350nm;
Figure 19 A is the height images of the tapping-mode AFM of PCL-TPE, resolving power 5 μm × 5 μm;
Figure 19 B is the cross-sectional outling figure of white dashed line in Figure 19 A;
Figure 20 is the XRD graphic representation of PCL3k-TPE Nano lamellite;
The DSC collection of illustrative plates that Figure 21 is PCL3k-TPE Nano lamellite in first time heat scan process;
Figure 22 is that PCL-TPE is with C 60 +as the TOF-SIMS collection of illustrative plates of primary ions bundle;
Figure 23 is that PCL-TPE is with Bi 3 +as the TOF-SIMS collection of illustrative plates of primary ions bundle;
Figure 24 is that PCL-TPE is with C 60 +as the TOF-SIMS collection of illustrative plates of primary ions bundle 65 DEG C time;
Figure 25 is the schematic diagram of the crystallisation process of being induced by the Nano lamellite of fluorescent polymer;
Figure 26 is that PCL-TPE is with the XPS collection of illustrative plates of 45 ° of angles of emergence;
Figure 27 is that PCL-TPE is with the XPS collection of illustrative plates of 25 ° of angles of emergence;
Figure 28 A is the PL spectrum of the PA (picricacid) adding different amount in PCL-TPE Nano lamellite suspension;
Figure 28 B is I 0the correlogram of/I value and the concentration of PA in PCL-TPE solution, the static cancellation constant of PCL-TPE Nano lamellite is 380,000L mol -1;
Figure 29 adds PA, toluene, 2,4-dinitrotoluene (DNT), 4-nitrophenols, 4-oil of mirbane, 2 bromo toluene, 1 respectively in PCL-TPE, the fluorescence intensity (I after 2 dichlorobenzenes, 1,2,4-tribromo-benzene, bromo-2-oil of mirbane, 3,5-dinitrobenzene ethanol 0/ I) variation diagram, and insert in PCL-TPE suspension the digital imagery figure adding above-mentioned different explosive substance analogue;
Figure 30 is PCL5k-TPE and THF/H 2in the solution of O mixed solvent (volume ratio 1:99), I 0the correlogram of/I value and different concns PA, coefficient R=0.9933; The static cancellation constant (K) of PCL5k-TPE is 122,000L mol -1;
Figure 31 is PCL10k-TPE and THF/H 2in the solution of O mixed solvent (volume ratio 1:99), I 0the correlogram of/I value and different concns PA, coefficient R=0.9944; The static cancellation constant (K) of PCL5k-TPE is 102,000L mol -1;
Figure 32 is PCL20k-TPE and THF/H 2in the solution of O mixed solvent (volume ratio 1:9), I 0the correlogram of/I value and different concns PA, coefficient R=0.9899; The static cancellation constant (K) of PCL20k-TPE is 61,000L mol -1;
Figure 33 is the variation diagram of the static cancellation constant (K) of the PCL with different quantities repeating unit.
Embodiment
Below in conjunction with drawings and Examples, activation luminescent material of the present invention and preparation method thereof is described further:
The present invention prepares tetraphenyl ethylene-CO by following reaction formula 2h (TPE-CO 2h) and by TPE-CO 2h and cyclodextrin (CD) condensation reaction form TPE-CDs inclusion compound (TPE-CDs) and activate luminescent material, comprise TPE-β-CD, TPE-α-CD and TPE-γ-CD inclusion compound.And purifying is carried out to the intermediate product in reaction process and end product, by nucleus magnetic resonance (NMR) spectrum and other spectrum a large amount of, these intermediate products and end product are characterized, and then confirm the molecular structure of its expection.Above-mentioned three kinds of TPE-CDs are all water-soluble, in dimethyl sulfoxide (DMSO) (DMSO) and dimethyl formamide (DMF).
Embodiment 1:
(1) structural formula of TPE-β-CD
(2) prepare TPE-beta-CD inclusion and activate luminescent material
In nitrogen environment, under 0 DEG C of condition, by 0.188g (0.5mmol) TPE-CO in 50ml round-bottomed flask 2h and 0.5675g (0.5mmol) β-CD is dissolved in 10ml anhydrous dimethyl formamide (DMF), the N containing 0.103g (0.5mmol) is added again after dissolving, the 5ml dry DMF of N-dicyclohexylcarbodiimide (dicyclohexylcarbodiimide, DCC); In nitrogen environment, warm temperature was to stirring reaction under room temperature condition 3 days; Filter, filtrate is dropwise added in a large amount of ether under the condition of vigorous stirring, separate out solids; And then filtering separation obtains this solids, oven dry that this solids is spent the night under vacuum 40 DEG C of conditions, productive rate 70%. 1H NMR(400MHz,DMSO-d 6),δ(TMS,ppm):3.28(d,7H,H 4),3.33(d,7H,H 2),3.55(d,7H,H 5),3.60(d,12H,H 6),3.64(br,7H,H 3),4.44(t,6H,O 6H),4.80(d,7H,H 1),5.65(s,7H,O 3H),5.70(d,7H,O 2H),7.93(s,2H,Ar-H). 13C NMR(400MHz,DMSO-d 6),δ(TMS,ppm):59.7(C 6),71.8(C 2),72.3(C 5),72.9(C 3),81.3(C 4),101.7(C 1),130.4(Ar),156.7(C＝C),162.2(C＝O).HRMS(MALDF-TOF):m/z1492.65(M +,calcd 1492.51)。
Embodiment 2:
(1) structural formula of TPE-α-CD:
(2) prepare TPE-α-CD inclusion compound and activate luminescent material
In nitrogen environment, under 0 DEG C of condition, by 0.188g (0.5mmol) TPE-CO 2h and 0.486g (0.5mmol) α-CD is dissolved in 15ml anhydrous dimethyl formamide (DMF), and adds 0.103g (0.5mmol) DCC as catalyzer; In nitrogen environment, warm temperature was to stirring reaction under room temperature condition 3 days; Filter, filtrate is dropwise added in a large amount of ether under the condition of vigorous stirring, separate out solids; And then filtering separation obtains solids, oven dry that solids is spent the night under vacuum 40 DEG C of conditions, productive rate 60%. 1H NMR(400MHz,DMSO-d 6),δ(TMS,ppm):3.30(m,6H,H 4),3.36(m,6H,H 2),3.56(d,6H,H 5),3.61(m,10H,H 6),3.75(t,6H,H 3),4.46(t,5H,O 6H),4.77(d,6H,H 1),5.41(d,6H,O 3H),5.50(d,6H,O 2H),7.93(s,2H,Ar-H). 13C NMR(400MHz,DMSO-d 6),δ(TMS,ppm):59.7(C 6),71.8(C 2),72.3(C 5),72.9(C 3),81.3(C 4),101.7(C 1),130.4(Ar),156.7(C＝C),162.2(C＝O).HRMS(MALDF-TOF):m/z 1330.63(M +,calcd 1330.45)。
Embodiment 3:
(structural formula of 1TPE-γ-CD:
(2) prepare TPE-γ-CD inclusion compound and activate luminescent material
In nitrogen environment, under 0 DEG C of condition, by 0.188g (0.5mmol) TPE-CO 2h, 0.648g (0.5mmol) γ-CD and 0.103g (0.5mmol) DCC is dissolved in 15ml anhydrous dimethyl formamide (DMF); In nitrogen environment, warm temperature was to stirring reaction under room temperature condition 3 days; Filter, filtrate is dropwise added in a large amount of ether under the condition of vigorous stirring, separate out solids; And then filtering separation obtains solids, oven dry that solids is spent the night under vacuum 40 DEG C of conditions, productive rate 52%. 1H NMR(400MHz,DMSO-d 6),δ(TMS,ppm):3.28(d,8H,H 4),3.33(d,8H,H 2),3.55(d,8H,H 5),3.60(d,16H,H 6),3.64(br,8H,H 3),4.44(t,7H,O 6H),4.80(d,8H,H 1),5.65(s,8H,O 3H),5.70(d,8H,O 2H),6.9-7.1(m,4H,Ar-H),7.93(s,2H,Ar-H). 13C NMR(400MHz,DMSO-d 6):δ(TMS,ppm):59.7(C 6),71.8(C 2),72.3(C 5),72.9(C 3),81.3(C 4),101.7(C 1),130.4(Ar),156.7(C＝C),162.2(C＝O).HRMS(MALDF-TOF):m/z 1654.40(M +,calcd 1654.56)。
Embodiment 4: to the structural identification of TPE-CDs and the experimental study of application aspect thereof
As shown in Figure 1, in the 2D ROESY NMR spectrum of TPE-β-CD, the NOE (nuclear overhauser enhancement) that can see between TPE proton and the inside proton in CD chamber intersects peak, close-coupled mutually between the inside proton showing TPE proton and CD chamber, also illustrates that the most of phenyl ring in TPE is fixed in CD chamber simultaneously.On the other hand, can't detect NOE peak-to-peak signal between the inside proton in the resonance peak in δ 7.9 position and β-CD chamber, this is due to the reason far away of position between them.As shown in Figures 2 and 3, can see that TPE-α-CD is similar to TPE-β-CD with the spectrum of TPE-γ-CD structural identification.In conjunction with the above results, show the geometry of TPE-β-CD and the optimization chemical structure of TPE by Fig. 4 A, 4B and 5 structural representations.
TPE-β-CD structure 1h NMR signal is concentration dependent, and as shown in Figure 6, in highly concentrated solution, the absorption peak of δ 7.1 and δ 6.9 position disappears, and shows the formation of intermolecular inclusion compound.In order to further confirmation, repeat NMR to measure when there is adamantine, as shown in Figure 7, after being mixed into adamantine, the absorption peak of δ 7.1 and δ 6.9 position obviously strengthens and manifests, and this is due to powerful between adamantine and CD and specifically interact and cause part phenyl ring to be extruded in β-CD chamber causing.
Size subsequently for CD chamber is studied for the impact of internal molecular motion restriction (restriction of intramolecular motions, RIM) process.Similar to TPE-β-CD, as shown in Figure 8, the dilute solution of TPE-α-CD demonstrates two broad peaks at δ 7.1 and δ 6.9 position, and these two peaks just disappear after by the thickening of TPE-α-CD solution.On the contrary, as shown in Figure 9, also still can observe in the strong solution of TPE-γ-CD and show the less-restrictive of γ-CD to TPE movement in the peak that δ 7.1 and δ 6.9 disposes.With the fignal center of δ 7.9 position for reference, TPE-α-CD is the most weak at the absorption peak of δ 7.1 and δ 6.9 position, and TPE-γ-CD is the strongest at the absorption peak of δ 7.1 and δ 6.9 position.See table 1, the size larger compared to γ-CD chamber, α-CD chamber size is less, greatly limit the motion of TPE phenyl ring, makes aromatic hydrocarbon signal weakening.
Table 1: the chamber size of cyclodextrin a
athe degree of depth of cyclodextrin: 0.78nm.
As shown in Figure 10, ultraviolet (UV) spectrum of TPE-CDs inclusion compound activation luminescent material shows it and has a wide absorption spectrum band at 314nm place, there is blue shift relative to not carrying the substituent TPE derivative (TPE-C2) of CD, showing that TPE adopts more guache conformations and then orders about TPE by hydrophobic interaction between TPE and CD and allocating into in CD chamber.Circular dichroism (circular dichroism) spectrum is used to confirm above-mentioned hydrophobic interaction.As shown in figure 11, TPE-CDs inclusion compound activate luminescent material circular dichroism spectrum in TPE absorption region in all there is a positive signal, show CD induce TPE be compressed into spiral-shaped structure.
Figure 12 A and Figure 12 B shows fluorescence (FL) spectrum that TPE-CDs inclusion compound activates luminescent material, the dilute solution of TPE makes in 470nm luminescence faint due to the internal molecular motion of phenyl ring in the methyl-sulphoxide (DMSO), and the internal molecular motion of phenyl ring effectively can expend the energy of excited state by non-radiative relaxation passage (nonradiative relaxation channels).And form sharp contrast, as shown in figure 13, TPE-β-CD is at the stronger fluorescence of 410nm display, and the 60nm compared to unsubstituted TPE fluorescence Spectra blue shift, Fluorescence Increasing shows the restriction that the athletic meeting of phenyl ring in TPE-β-CD is subject to some and is formed from inclusion compound.TPE in CD chamber has guache conformation more, therefore causes the blue shift of fluorescence.Compared with TPE-α-CD, TPE-β-CD shows more weak fluorescence at 410nm, but more luminous than TPE-γ-CD strong.Under identical experiment condition, the physical mixture solution being dissolved in TPE and the CD of DMSO is weak at 470nm radioluminescence.By measuring the quantum yield that TPE-CDs inclusion compound activates luminescent material and TPE and CD physical mixture respectively in contrast with Quinine Sulphate Di HC; unsubstituted TPE shows low quantum yield (0.5%) in DMSO; and the quantum yield of TPE-β-CD mixture exceeds 20 times of values than unsubstituted TPE; by mixing with adamantine; this value also can be higher; the chances are for this because the adamantine of comparatively large vol can movement limit (restriction of intramolecular motions, RIM) process in further activating molecules.Compared to the γ-CD chamber of large-size, the α-CD chamber of reduced size more effectively can limit the motion of phenyl ring, and therefore activate in luminescent material at TPE-CDs inclusion compound, the quantum yield of the fluorescence of TPE-α-CD is the highest.Because the quantum yield of the physical mixture of TPE and various CD is all lower, illustrate that the covalent attachment between TPE and CD is most important for the formation of inclusion compound.TPE and CD is fused into a molecule, and the two is close to each other, makes the easier inclusion of phenyl ring in CD chamber.
For confirming luminescence enhancement mechanism further, carry out time resolved fluorescence experiments of measuring.As shown in Figure 14 and table 2, the luminous intensity of unsubstituted TPE is exponentially successively decreased, and luminescent lifetime is 1.41ns; By contrast, TPE-β-CD excited state luminous intensity mainly relaxes along slow path successively decreases, and luminescent lifetime is 8.23ns.In unsubstituted TPE solution, active internal molecular motion buries in oblivion the energy of excited state effectively, causes obviously shortening fluorescent lifetime; On the other hand, in TPE-beta-CD inclusion, the motion of TPE is restricted, and this will hinder radiationless mitigation path and increases the excitability electronics suffering attenuation, therefore makes luminescent lifetime longer.The time resolved fluorescence spectrum of TPE-α-CD is similar to TPE-β-CD, and the luminescent lifetime of TPE-γ-CD is shorter than unsubstituted TPE.
Table 2. is dissolved in the luminescent lifetime a of TPE-CDs inclusion compound in DMSO and unsubstituted TPE
adetermined by I, I=A 1exp (-t/ τ 1)+A 2exp (-t/ τ 2).
Utilize high quantum production rate and TPE and CD self the preferably biocompatibility of TPE-CDs inclusion compound, TPE-CDs inclusion compound is applied to field of biology.As shown in figs. 15a and 15b, the tenuigenin of the HeLa cell cultivated with TPE-β-CD have issued uviolizing, shows that TPE-β-CD can penetrate into cytolemma, can be used as fluorescent visual agent for imaging in cell.
The present invention passes through following reaction formula by TPE-CO 2h and poly-epsilon-caprolactone (PCL) condensation reaction form PCL-TPE Nano lamellite and activate luminescent material, comprise PCL3k-TPE, PCL5k-TPE, PCL10k-TPE and PCL20k-TPE.And purifying is carried out to the intermediate product in reaction process and end product, by nucleus magnetic resonance (NMR) spectrum and gel permeation chromatography (GPC), these intermediate products and end product are characterized, and then confirm the molecular structure of its expection.PCL-TPE polymkeric substance is all dissolved in common solvent, as THF, acetone, DCM, DMSO and DMF.
Embodiment 5:
(1) structural formula of PCL3k-TPE:
(2) method that PCL3k-TPE polymkeric substance activates luminescent material is prepared
In nitrogen environment, under 0 DEG C of condition, by 0.302g (0.8mmol) TPE-CO in 50ml round-bottomed flask 2h and 0.32g (0.1mmol) PCL3k is dissolved in 10ml anhydrous dimethyl formamide (DMF), the N containing 0.041g (0.2mmol) is added again after dissolving, the 5ml dry DMF of N-dicyclohexylcarbodiimide (dicyclohexylcarbodiimide, DCC); In nitrogen environment, warm temperature was to stirring reaction under room temperature condition 3 days; Filter, filtrate is dropwise added in a large amount of ether under the condition of vigorous stirring, separate out solids; And then filtering separation obtains solids, oven dry that solids is spent the night under vacuum 40 DEG C of conditions, productive rate 82%. 1H NMR(400MHz,CDCl 3),δ(TMS,ppm):1.37(m,56H,COOCH 2CH 2CH 2),1.64(d,112H,COOCH 2CH 2CH 2CH 2),2.30(t,56H,COCH 2),3.64(t,3H,CH 2OH),4.05(t,53H,OCH 2),4.26(s,4H,OCH 2from initiator).6.9-7.1(s,1H,Ar-H),7.93(br,8H,Ar-H)。Embodiment 6:
(1) structural formula of PCL5k-TPE:
(2) PCL5k-TPE polymkeric substance activates the preparation method of luminescent material:
In nitrogen environment, under 0 DEG C of condition, by 0.302g (0.8mmol) TPE-CO in 50ml round-bottomed flask 2h and 0.46g (0.1mmol) PCL5k is dissolved in 10ml anhydrous dimethyl formamide (DMF), the N containing 0.041g (0.2mmol) is added again after dissolving, the 5ml dry DMF of N-dicyclohexylcarbodiimide (dicyclohexylcarbodiimide, DCC); In nitrogen environment, warm temperature was to stirring reaction under room temperature condition 3 days; Filter, filtrate is dropwise added in a large amount of ether under the condition of vigorous stirring, separate out solids; And then filtering separation obtains solids, oven dry that solids is spent the night under vacuum 40 DEG C of conditions, productive rate 87%. 1H NMR(400MHz,CDCl 3),δ(TMS,ppm):1.37(m,80H,COOCH 2CH 2CH 2),1.64(d,160H,COOCH 2CH 2CH 2CH 2),2.30(t,80H,COCH 2),3.64(t,4H,CH 2OH),4.05(t,76H,OCH 2),4.26(s,4H,OCH 2from initiator),6.9-7.1(s,1H,Ar-H),7.93(br,8H,Ar-H)。
Embodiment 7:
(1) structural formula of PCL10k-TPE:
(2) PCL10k-TPE polymkeric substance activates the preparation method of luminescent material:
In nitrogen environment, under 0 DEG C of condition, by 0.302g (0.8mmol) TPE-CO in 50ml round-bottomed flask 2h and 0.93g (0.1mmol) PCL10k is dissolved in 10ml anhydrous dimethyl formamide (DMF), the N containing 0.041g (0.2mmol) is added again after dissolving, the 5ml dry DMF of N-dicyclohexylcarbodiimide (dicyclohexylcarbodiimide, DCC); In nitrogen environment, warm temperature was to stirring reaction under room temperature condition 3 days; Filter, filtrate is dropwise added in a large amount of ether under the condition of vigorous stirring, separate out solids; And then filtering separation obtains solids, oven dry that solids is spent the night under vacuum 40 DEG C of conditions, productive rate 89%. 1H NMR(400MHz,CDCl 3),δ(TMS,ppm):1.37(m,164H,COOCH 2CH 2CH 2),1.64(d,328H,COOCH 2CH 2CH 2CH 2),2.30(t,164H,COCH 2),3.64(t,4H,CH 2OH),4.05(t,160H,OCH 2),4.26(s,4H,OCH 2from initiator),6.9-7.1(s,1H,Ar-H),7.93(br,8H,Ar-H)。
Embodiment 8:
(1) structural formula of PCL20k-TPE:
(2) PCL20k-TPE polymkeric substance activates the preparation method of luminescent material:
In nitrogen environment, under 0 DEG C of condition, by 0.302g (0.8mmol) TPE-CO in 50ml round-bottomed flask 2h and 1.78g (0.1mmol) PCL20k is dissolved in 10ml anhydrous dimethyl formamide (DMF), the N containing 0.041g (0.2mmol) is added again after dissolving, the 5ml dry DMF of N-dicyclohexylcarbodiimide (dicyclohexylcarbodiimide, DCC); In nitrogen environment, warm temperature was to stirring reaction under room temperature condition 3 days; Filter, filtrate is dropwise added in a large amount of ether under the condition of vigorous stirring, separate out solids; And then filtering separation obtains solids, oven dry that solids is spent the night under vacuum 40 DEG C of conditions, productive rate 85%. 1H NMR(400MHz,CDCl 3),δ(TMS,ppm):1.37(m,312H,COOCH 2CH 2CH 2),1.64(d,624H,COOCH 2CH 2CH 2CH 2),2.30(t,312H,COCH 2),3.64(t,4H,CH 2OH),4.05(t,308H,OCH 2),4.26(s,4H,OCH 2from initiator),6.9-7.1(s,1H,Ar-H),7.93(br,8H,Ar-H)。
The relevant physicochemical characteristic of embodiment 9:PCL-TPE and structural identification and application aspect
Experimental study
See table 3, in the molecular weight and molecualr weight distribution showing PCL and PCL-TPE
Mass percent shared by TPE.
Mass percent in the table molecular weight and molecualr weight distribution of 3:PCL and PCL-TPE shared by TPE
Wherein, aby 1h NMR measures;
cobtained by GPC measure and calculation in contrast with polystyrene;
ddP represents the polymerization degree (degree of polymerization), by PCL's 1h NMR composes mensuration, by formula DP=2n=2I c/ I acalculate, wherein I aand I crepresent the integration of 4.26 and 2.30 place's resonance peaks in proton nmr spectra respectively;
et represents the whole ratio (termination ratio of PCL with TPE) of PCT and TPE, passes through T=I a/ I ccalculate and measure, wherein I aand I crepresent the integration of 7.93 and 4.26 place's resonance peaks in proton nmr spectra respectively;
fw represents the mass percent in PCL-TPE shared by TPE, passes through W=2TM tPE/ (M pCL+ 2M tPE) calculate, wherein M tPEand M pCLbe respectively the molecular weight of TPE and PCL.
As shown in Figure 16,17A and 17B, and see table 4, by dsc (differential scanning calorimetry, DSC) hydrate ferric chloride of PCL-TPE is investigated, in cooling scanning process, 37.2 DEG C of place PCL-TPE show obvious exothermic peak, think PCL crystallization; PCL crystalline fusion in ensuing heat scan process, 52.3 DEG C of places can observe sharp-pointed endotherm(ic)peak.The degree of crystallinity estimation of PCL-TPE is 55.9%, and these data presentation PCL-TPE are crystallizable as expection.
Show the Tc of 4:PCL-TPE, melt temperature, fusion enthalpy and degree of crystallinity
The Δ H of desirable PCL crystallization is 142.9J/g; Degree of crystallinity (the X of PCL-TPE c) pass through X c=Δ H/ [142.9* (1-W)] calculates, and wherein W represents the mass percent that TPE is shared in PCL-TPE.
PCL-TPE in solid form time can High Efficiency Luminescence, and radiation dies down after being dissolved in solvent, as being dissolved in THF, therefore investigate the Fluorescence behaviour of PCL-TPE in THF/ water mixed solvent, as shown in figures 18a and 18b, in THF/ water mixed solvent, during volume ratio≤80% of water, PCL-TPE luminescence is weak; When the volume ratio of water is increased to 99%, the luminous intensity of PCL-TPE strengthens suddenly at 480nm, shows typical polymerisation induced luminescence (AIE) phenomenon.
Characterize PCL-TPE by atomic force microscopy (atomic force microscopy, AFM) and be suspended in form in aqueous medium, in Figure 19 A, the height image of tapping-mode AFM shows the lamellar structure of PCL-TPE; The cross-sectional outling figure of Figure 19 B shows the about 7nm of its thickness, close to the thickness of PCL platelet.In order to investigate the microstructure of PCL-TPE Nano lamellite further, PCL-TPE suspension solution carried out centrifugal and filter acquisition PCL-TPE Nano lamellite powder, as shown in figure 20, X-ray diffraction (XRD) collection of illustrative plates is 21.3 ° and 23.6 ° of displays, two obvious diffraction peaks, 110 diffraction planes of crystallization orthogonal to PCL are relevant with 200 diffraction planes respectively, show PCL crystallization.As shown in figure 21, the DSC collection of illustrative plates for the first time in heat scan process shows a sharp-pointed endotherm(ic)peak, confirms the crystallization of PCL further.
Utilize time of flight secondary ion massspectrometry (time-of – flight secondary ion mass spectrometry, TOF-SIMS) to analyze the surface composition of PCL-TPE platelet, as shown in figure 22, this TOF-SIMS composes display C 60 +as primary ions bundle, detect PCL trunk and the TPE terminal group being positioned at PCL trunk end, see table 5, the C of PCL trunk 3h 3o fragment carbonium m/z=55; TPE terminal group m/z=357.
The peak ownership of the TOF-SIMS spectrum of table 5:PCL-TPE nanometer sheet
In order to measure the distribution along depth direction TPE, using and comparing C 60 +little Bi 3 +as primary ions bundle, normal conditions it is believed that the degree of depth penetrated under same ion dosage is relevant with the size of primary ions bundle, tuftlet ion penetration darker.As shown in figure 23, PCL-TPE uses Bi 3 +as TOF-SIMS spectrum and the use C of primary ions bundle 60 +as primary ions bundle TOF-SIMS spectrum similar, but attract people's attention be use Bi 3 +ratio as the peak strength of m/z=357 during primary ions bundle and the peak strength of m/z=55 is 5 × 10 -3, than use C 60 +as the ratio 22.9 × 10 during primary ions bundle -3low many, this shows the increase along with penetration depth, and shared by TPE, content sharply reduces, and illustrates that TPE is positioned on the surface of PCL-TPE Nano lamellite.
Because the structure of PCL-TPE Nano lamellite is relevant with temperature, therefore under 65 DEG C of conditions higher than PCL-TPE melt temperature (52.3 DEG C), TOF-SIMS detection is carried out, as shown in figure 24,65 DEG C time, the ratio of the peak strength of the m/z=357 of PCL-TPE and the peak strength of m/z=55 is 4.4 × 10 -3, than ratio 22.9 × 10 at room temperature -3low many, show that the TPE being at high temperature positioned at Nano lamellite surface can internally spread, PCL platelet meeting melting under the condition higher than PCL-TPE melt temperature, by the driving of concentration gradient, TPE internally moves, and therefore demonstrates PCL-TPE Nano lamellite structure as shown in figure 25.
In order to confirm the distribution situation of TPE in PCL-TPE platelet further, see table 6 and Figure 26, x-ray photoelectron power spectrum (XPS) is used to verify, as is expected, PCL-TPE platelet detects carbon and oxygen element, detects oxygen level in PCL-TPE (oxygen fraction) for 20.1% with 45 ° of angles of emergence (takeoff angle); As shown in figure 27, during reduction angle of emergence to 25 °, detection obtains oxygen level and is reduced to 16.5%, shows that the TPE of anoxic has stayed on the surface of PCL-TPE platelet.In addition, angle of emergence is reduced to 25 ° from 45 °, sp 2carbon content is increased to 64.5% from 40.1%, shows that TPE is positioned at the interface of polymkeric substance/air.
Table 6: the oxygen level of the PCL-TPE nanometer sheet detected during different angle of emergence and sp 2carbon content
The result of TOF-SIMS and XPS spectrum all means carries out in the process of crystallization at PCL, and TPE terminal group is ostracised outside PCL crystal, makes due to TPE and polymkeric substance covalent attachment and is suspended on the surface.The possible cause that on polymkeric substance platelet, TPE is exposed is caused to have three: the low compatibility between (1) hydrophobic aromatic series TPE and hydrophilic aliphatics caprolactone fragment; (2) size of large volume TPE and PCL structure cell do not match (a=0.748nm, b=0.498nm, c=1.726nm); (3) TPE has higher transport property as terminal group, can not be absorbed in sheet intracrystalline in polymer crystallization process.In fact, up to the present still the relevant report to polymer sheet intracrystalline can be absorbed in, even if little terminal group, as sulfydryl, hydroxy, carboxyl, benzyl etc. about terminal group, sheet intracrystalline can not be entered to and be positioned at platelet on the surface, much larger than above-mentioned group of TPE.The TPE that this demonstrates Figure 25 signal is exposed to structure outside PCL-TPE platelet.
Utilize the TPE hung on the surface, use PCL-TPE Nano lamellite can detection of explosives.Suspendible PCL-TPE Nano lamellite is in an aqueous medium based on luminous at 350nm radiation high-efficiency, and after adding trinitrophenol (picric acid, PA), luminescence weakens gradually.As seen in figs. 28 a and 28b, along with the increase of PA concentration, I 0the ratio of/I linearly reduces, and silent (Stern-Volmer) formula: the I in Si Ente-Wal is followed in the cancellation adding the PCL-TPE of trinitrophenol 0/ I=1+K [Q], wherein I 0the fluorescence intensity not adding quencher and add steady state after quencher is respectively with I; K represents to write from memory (Stern-Volmer) constant in Si Ente-Wal, and represent the sensitivity of fluorescent material to quencher, K value means more greatly the sensitivity of quencher higher.The K value of PCL-TPE Nano lamellite is 380000L/mol, much larger than the K value (K<20000L/mol) of fluorescence chemical sensor of gathering Silole (polysiloles) based on linear pattern.The static cancellation constant of height of PCL-TPE is relevant with the new texture that the TPE of Nano lamellite is exposed to its surface.
Further research PCL-TPE Nano lamellite is to the fluorescent reaction of explosive substance analogue.Blank PCL-TPE sends strong blue light under 365nm radiation, after adding equimolar PA, and blue light cancellation.But add equimolar PA analogue respectively, as toluene (Tol), 2,4-dinitrotoluene (DNT) (DNT), 4-nitrophenols (NP), 4-oil of mirbane (NB), 2 bromo toluene (BT), 1,2 dichlorobenzenes (DCB), 1,2,4-tribromo-benzene (TBB), bromo-2-oil of mirbane (BNB), 3,5-dinitrobenzene ethanol (DNBA) etc., still can observe with the naked eye the luminescence of PCL-TPE suspension.Figure 29 shows in PCL-TPE I when adding PA and its analogue respectively 0the ratio of/I, adds the I of PA 0the ratio of/I is much larger than adding other analogue, and show that PCL-TPE Nano lamellite has the characteristic of splendid selectivity antagonism PA analogue, therefore PCL-TPE can specific recognition PA.
Research PCL-TPE molecular weight is on the impact of cancellation constant (K), and as shown in figs. 30-33, along with the increase of PCL-TPE molecular weight, K value reduces, and possible reason is that the grafting density between TPE and PCL platelet is relevant with PCL-TPE molecular weight.Low-molecular-weight PCL-TPE has high TPE grafting density and then forms fluorescence nano platelet because content shared by TPE is higher, after adding PA, the TPE molecular luminescence cancellation that PA molecule makes some adjacent, causes higher detection sensitivity; For high molecular PCL-TPE, make TPE be isolated in separately on the surface of polymkeric substance platelet because content shared by TPE is lower, in order to make the luminous cancellation of independent TPE, this just needs the PA molecule of more, and then causes cancellation constant low.
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 (9)

1. activate a luminescent material, its structural formula is as follows:
Wherein, R 1group is cyclodextrin or poly-epsilon-caprolactone, and described poly-epsilon-caprolactone has 28-156 repeating unit; R 2, R 3and R 4group is selected from C respectively nh 2n+1, C 10h 7, C 12h 9, OC 6h 5, OC 10h 7, OC 12h 9, C nh 2nnCS, C nh 2nn 3, C nh 2nnH 2, C nh 2ncl, C nh 2nbr, C nh 2ni, wherein n=0 ~ 20.
2. activation luminescent material according to claim 1, is characterized in that, described R 1group is cyclodextrin, and described activation luminescent material can be used for the fluorescent visual agent preparing stain living cells.
3. activation luminescent material according to claim 1, is characterized in that, described R 1group is poly-epsilon-caprolactone, and described activation luminescent material can be used for detection of explosives.
4. activate a preparation method for luminescent material, it is characterized in that, comprise the following steps:
A, in nitrogen environment, under cold condition, by R 1the compound of group, tetraphenyl ethylene-CO 2h (TPE-CO 2h) and N, N-dicyclohexylcarbodiimide be dissolved in anhydrous dimethyl formamide;
B, in nitrogen environment, warm temperature is to stirring reaction under room temperature condition until reacted;
C, filtration, be dropwise added in a large amount of ether by the filtrate obtained under the condition of vigorous stirring, separates out solids;
D, again filtering separation obtain this solids, are dried under vacuum by this solids, obtain activating luminescent material.
5. the preparation method of activation luminescent material according to claim 4, is characterized in that, in step, and described R 1the compound of group is cyclodextrin, described cyclodextrin, tetraphenyl ethylene-CO 2h (TPE-CO 2h) and the mol ratio of N, N-dicyclohexylcarbodiimide be 1:1:1, the molecular volume of described cyclodextrin in anhydrous dimethyl formamide is than being 1:30.
6. the preparation method of activation luminescent material according to claim 4, is characterized in that, in step, and described R 1group compound is poly-epsilon-caprolactone, described poly-epsilon-caprolactone, tetraphenyl ethylene-CO 2h (TPE-CO 2h) and the mol ratio of N, N-dicyclohexylcarbodiimide be 1:8:2, the molecular volume of described poly-epsilon-caprolactone in anhydrous dimethyl formamide is than being 1:150.
7. the preparation method of activation luminescent material according to claim 4, is characterized in that, in step, described cold condition is 0 DEG C.
8. the preparation method of activation luminescent material according to claim 4, is characterized in that, in stepb, in nitrogen environment, warm temperature was to stirring reaction under room temperature condition 3 days.
9. the preparation method of activation luminescent material according to claim 4, is characterized in that, in step D, bake out temperature is 40 DEG C.
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