CN107793421A - Probe with aggregation-induced emission characteristic and its preparation method and application - Google Patents
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Abstract
The present invention proposes a kind of probe with aggregation-induced emission characteristic and its preparation method and application, and the probe includes：Wherein, each R independently chooses from H, alkyl, unsaturated alkyl, miscellaneous alkyl, cycloalkyl, Heterocyclylalkyl, aryl and heteroaryl；X is the chromophore being bonded with aggregation inducing transmitting fluorogen.The probe high sensitivity of the present invention, it is practical.
Description
Technical field
The present invention relates to detection Material Field, more particularly to a kind of ratio metering type with aggregation-induced emission characteristic to visit
Pin and its preparation method and application.
Background technology
Due to having made section with high sensitivity, Noninvasive and good spatial and temporal resolution, luminescence generated by light (PL) technology
Scholar has been fascinated many decades in the various fields such as chemical co-ordination, environmental science, bio-imaging and medical diagnosis.Some are all
The radioactivity shiner that such as BODIPY, fluorescein and rhodamine frequently use presents relatively small Stokes shift (one
As be less than 30nm), this may cause some practical problems, including notorious inside filter effect and exciting light and transmitting
Interference between light.FRET (FRET) is always a kind of powerful instrument, can provide layout strategy, and it is not
It is only used for fluorescent dye of the research and development with big pseudo- Stokes shift, it may also be used for polychrome senses and imaging.
FRET systems include the donor and acceptor generally connected by flexible aliphatic sept.FRET efficiency is main
Adjusted by changing three parameters：1) distance of donor and acceptor (rDA)；2) the absorption light of the emission spectrum of donor and acceptor
Overlap integral (J) between spectrum；3) relative orientation of donor emission dipole moment and acceptor absorbance dipole moment.FRET extensively should
For many applications, such as the light collection of artificial photosynthesis and solar cell, chemical sensing, DNA or protein conformation change
Monitoring and Enzyme assay.
However, in order to realize big pseudo- Stokes shift, the spectra overlapping between donor emission and acceptor absorbance may
It can weaken, this is by the reduction for causing FRET efficiency and the leakage of donor emission.Burgess and colleague have developed across bond energy amount
(TBET) mechanism of transfer, it can be as the valuable method for solving this antinomy.In TBET systems, donor and acceptor lead to
The flexible aliphatic connector connection crossed in rigid connection body rather than FRET systems.It should be noted that although donor and by
Body is generally by being conjugated group (being usually phenyl ring, double or triple bonds) connection, but the twist angle between donor and acceptor is big, this
Them are hindered to turn into fluorogen.Rate of energy transfer in TBET systems can be higher by 2 than the rate of energy transfer of traditional FRET systems
The individual order of magnitude, so that it less depends on spectra overlapping.Therefore, even if spectra overlapping is smaller, TBET mechanism can also be passed through
High energy transfer efficiency (ETE) is easily realized, this is very useful to producing big pseudo- Stokes shift.
Recently, normal and colleague proposes a kind of new FRET systems for being referred to as dark-state Resonance energy transfer (DRET), and it is wrapped
Containing with low quantum yield (<1%) dark-state donor.Fluorescent dye in DRET storehouses shows noticeable property, such as
The adjustable transmission of single-shot and big pseudo- Stokes shift.Significantly, since the quantum yield of donor is low, observation
Less than background influence, this causes the dyestuff in DRET collection of illustrative plates to turn into the ideal candidate of biologic applications.However, the energy of DRET dyestuffs
Amount transfer efficiency nevertheless suffers from the strong influence of spectra overlapping.Therefore, the selection of donor and acceptor may be by DRET systems
Limitation.In addition, when the non-radiative decay speed of dark-state donor is enough near can be compared with the energy transfer rat that resonates when, energy turns
Efficiency is moved to be likely to reduced.TBET mechanism is introduced in dark-state energy transfer system can be used as a kind of more effectively strategy, because
TBET speed relative to non-radiative decay be it is quick, and energy transfer efficiency limited by spectra overlapping it is smaller.In addition, by
It is low in the quantum yield of donor, it can realize that open type senses by DRET mechanism.Due to fluorescence intensity substantially by dye strength,
The influence of exciting power intensity and other environmental factors, turn on sensor are difficult to provide the quantitative information about analyte.At this
Aspect, ratio metering type probe would be even more beneficial to quantitative detection, because the self calibration of their two wavelength allowable is above-mentioned to eliminate
Most of interference.
Aggregation-induced emission (AIE) dyestuff can show nothing or weak PL signals in the solution, but show in the collected state
Go out strong fluorescent emission, compared with generally the conventional dyes of (ACQ) effect are quenched as caused by undesired aggregation in display, this
It is antipodal phenomenon.AIE mechanism is attributed to internal molecular motion (RIM) limitation, and the luminescent substance with AIE properties has
There is excellent feature, such as solid-state high brightness and excellent photostability.Therefore, aggregation-induced emission thing is a kind of new material,
There is practicality including fields such as OLED, bio-imaging and chromatograms.Therefore, it is probably to produce newly with reference to AIE and TBET mechanism
The very promising direction of material.In these AIE cores, tetraphenylethylene (TPE) is due to being readily synthesized, solid luminescent, easily
In modification, the advantages that adjustable transmission and other functions can be realized, obtain most widely used.
The content of the invention
The present invention relates to across the key energy transfer of the new dark-state based on TPE derivatives and rhodamine part (DTBET) strategy.
Because TBET speed is fast, the energy of dark-state TPE derivatives is substantially transferred to rhodamine part, ETE before non-radiative decay release
Up to 99%.The present invention studies the structure-performance relation of DTBET processes and DTBET boxes by carrying out quantum chemistry calculation.
Further, since the emission characteristics of TPE derivatives in solids, the present invention, which has designed and synthesized, has high selectivity and high sensitivity
Hg2+With HClO ratio metering type probe.
Technical scheme proposed by the invention is as follows：
On the one hand, the present invention proposes a kind of ratio metering type probe with aggregation-induced emission characteristic, the probe
Including：
Wherein, each R is independently from H, alkyl, unsaturated alkyl, miscellaneous alkyl, cycloalkyl, Heterocyclylalkyl, aryl and heteroaryl
Chosen in base；X is the chromophore being bonded with aggregation inducing transmitting fluorogen.
Specifically, in the above-mentioned probe of the present invention, it is characterised in that X is：
Wherein, each R is independently from H, alkyl, unsaturated alkyl, miscellaneous alkyl, cycloalkyl, Heterocyclylalkyl, aryl and heteroaryl
Chosen in base；Y is O or Si；Z is that aggregation inducing launches fluorogen.
Specifically, in the above-mentioned probe of the present invention, X is：
Wherein, Y is O or Si；Z is that aggregation inducing launches fluorogen.
Specifically, in the above-mentioned probe of the present invention, the probe is：
Wherein, R1、R2And R3Separately from H, alkyl, unsaturated alkyl, miscellaneous alkyl, cycloalkyl, Heterocyclylalkyl, virtue
Chosen in base and heteroaryl；Y is O or Si；Z is that aggregation inducing launches fluorogen.
Specifically, in the above-mentioned probe of the present invention, R1、R2And R3It is substituted or unsubstituted, and independently selected from
CnH2n+1、C10H7、C12H9、OC6H5、OC10H7、OC12H9、CnH2nNOH、CnH2nCOOH、CnH2nNCS、CnH2nN3、CnH2nNH2、
CnH2nSO3、CnH2nCl、CnH2nBr、CnH2nI andWherein, n values are in 0 to 20；
R ' is from CnH2nNCS、CnH2nN3、CnH2nNH2、CnH2nCl、CnH2nBr、CnH2nI andMiddle selection.
Specifically, in the above-mentioned probe of the present invention, probe m-TPE-RNS, i.e.,：
Specifically, in the above-mentioned probe of the present invention, probe p-TPE-RNS, i.e.,：
Specifically, in the above-mentioned probe of the present invention, probe is used to detect the trace Hg in water or active somatic cell2+。
Specifically, in the above-mentioned probe of the present invention, probe is used to detect exogenous HClO or endogenous HClO, and for dividing
Distinguish cancer cell and normal cell.
The invention also provides a kind of preparation method of probe, comprise the following steps：
Step S1, p-RBr is dissolved in ethanol, adds a hydrazine hydrate, reaction generation p-RHZ；
Step S2, by p-RHZ, TPE-B (OH)2、Pd(PPh3)4And K2CO3Mixing, then in a nitrogen atmosphere add THF and
H2O, reaction generation p-TPE-RHZ；
Step S3, p-TPE-RHZ, isothiocyanic acid benzene methyl and triethylamine are mixed, in a nitrogen atmosphere reaction generation p-
TPE-RNS；
Wherein, p-RBr chemical formula is：
P-RHZ chemical formula is：
P-TPE-RHZ chemical formula is：
P-TPE-RNS chemical formula is：
In the above-mentioned preparation method of the present invention, in step sl, p-RBr is dissolved in ethanol, after adding a hydrazine hydrate, led to
Stirring, backflow are crossed, is evaporated under reduced pressure and removes solvent；Remove the residue after solvent to purify by silica gel chromatographic column, so as to obtain p-
RHZ。
In the above-mentioned preparation method of the present invention, step S2 includes：
By p-RHZ, TPE-B (OH)2、Pd(PPh3)4And K2CO3It is placed in one or two neck flask；Two neck flasks are vacuumized simultaneously
Nitrogen is filled with, then adds THF and H2O, flowed back；
THF is removed under vacuo again, then with DCM and H2O carries out liquid separation extraction；DCM is removed to extract, then will be removed
Residue after DCM is purified by silica gel column chromatography, so as to obtain p-TPE-RHZ.
In the above-mentioned preparation method of the present invention, step S3 includes：
P-TPE-RHZ, isothiocyanic acid benzene methyl and triethylamine are dissolved in DMF, and stirred in a nitrogen atmosphere, then is passed through
Solvent is removed in vacuum；Remove the residue obtained after solvent to purify by silica gel chromatographic column, so as to obtain p-TPE-RNS.
The invention also provides a kind of preparation method of probe, comprise the following steps：
Step S1, m-RBr is dissolved in ethanol, adds a hydrazine hydrate, reaction generation m-RHZ；
Step S2, by m-RHZ, TPE-B (OH)2、Pd(PPh3)4And K2CO3Mixing, then in a nitrogen atmosphere add THF and
H2O, reaction generation m-TPE-RHZ；
Step S3, m-TPE-RHZ, isothiocyanic acid benzene methyl and triethylamine are mixed, in a nitrogen atmosphere reaction generation m-
TPE-RNS；
Wherein, m-RBr chemical formula is：
M-RHZ chemical formula is：
M-TPE-RHZ chemical formula is：
M-TPE-RNS chemical formula is：
In the above-mentioned preparation method of the present invention, in step sl, m-RBr is dissolved in ethanol, after adding a hydrazine hydrate, led to
Stirring, backflow are crossed, is evaporated under reduced pressure and removes solvent；Remove the residue after solvent to purify by silica gel chromatographic column, so as to obtain m-
RHZ。
In the above-mentioned preparation method of the present invention, step S2 includes：
By m-RHZ, TPE-B (OH)2、Pd(PPh3)4And K2CO3It is placed in one or two neck flask；Two neck flasks are vacuumized simultaneously
Nitrogen is filled with, then adds THF and H2O, flowed back；
THF is removed under vacuo again, then with DCM and H2O carries out liquid separation extraction；DCM is removed to extract, then will be removed
Residue after DCM is purified by silica gel column chromatography, so as to obtain m-TPE-RHZ.
In the above-mentioned preparation method of the present invention, step S3 includes：
M-TPE-RHZ, isothiocyanic acid benzene methyl and triethylamine are dissolved in DMF, and stirred in a nitrogen atmosphere, then is passed through
Solvent is removed in vacuum；Remove the residue obtained after solvent to purify by silica gel chromatographic column, so as to obtain m-TPE-RNS.
The invention also provides the trace Hg in a kind of water or active somatic cell2+Detection method, comprise the following steps：
Step S1, water sample or active somatic cell sample are dyed using probe as described above；
Step S2, the photoluminescence spectra of the water sample being colored or active somatic cell sample is made；And according to luminescence generated by light light
Spectrum detection trace Hg2+。
In the above-mentioned detection method of the present invention, probe is m-TPE-RNS or p-TPE-RNS；
Step S2 comprises the following steps：
Calculate in the photoluminescence spectra of the water sample that is colored or active somatic cell sample under 355nm the exciting of UV lamp
The ratio between photoluminescence intensity, i.e. PL intensity ratio under photoluminescence intensity and 480nm under 595nm；
Hg is determined according to PL intensity ratio2+Concentration.
The invention also provides the trace Hg in a kind of active somatic cell2+Detection method, comprise the following steps：
Step S1, active somatic cell sample is dyed using probe as described above；
Step S2, fluorescence is made to the active somatic cell sample being colored using common focus point migration Laser Scanning Confocal Microscope to be total to
Focus on micro-image；And trace Hg is detected according to fluorescence co-focusing micro-image2+。
The invention also provides the trace ClO in a kind of water or active somatic cell-Detection method, comprise the following steps：
Step S1, water sample or active somatic cell sample are dyed using probe as described above；
Step S2, the photoluminescence spectra of the water sample being colored or active somatic cell sample is made；And according to luminescence generated by light light
Spectrum detection trace ClO-。
In the above-mentioned detection method of the present invention, probe p-TPE-RNS；
Step S2 comprises the following steps：
Calculate in the photoluminescence spectra of the water sample that is colored or active somatic cell sample under 355nm the exciting of UV lamp
The ratio between photoluminescence intensity, i.e. PL intensity ratio under photoluminescence intensity and 485nm under 595nm；
ClO is determined according to PL intensity ratio-Concentration.
The invention also provides the trace ClO in a kind of active somatic cell-Detection method, comprise the following steps：
Step S1, active somatic cell sample is dyed using probe as described above；
Step S2, fluorescence is made to the active somatic cell sample being colored using common focus point migration Laser Scanning Confocal Microscope to be total to
Focus on micro-image；And trace ClO is detected according to fluorescence co-focusing micro-image-。
The invention also provides a kind of cancer cell and the resolving method of normal cell, comprise the following steps：
Step S1, biopsy sample is dyed using probe as described above；
Step S2, the fluoroscopic image for the biopsy sample that shooting is colored；Cell is different glimmering according to fluoroscopic image
Luminous intensity realizes the resolution to cancer cell and normal cell.
On the other hand, the present invention proposes a ratio metering type probe with aggregation-induced emission characteristic, the spy
Pin includes the one or more chromophories being bonded with one or more aggregation inducings transmitting fluorogen；Probe includes one or more
Skeleton structure, the skeleton structure are selected from：
Wherein, each R is independently from H, alkyl, unsaturated alkyl, miscellaneous alkyl, cycloalkyl, Heterocyclylalkyl, aryl and heteroaryl
Chosen in base；X is one or more chromophories for being bonded with one or more aggregation inducings transmitting fluorogen.
In the above-mentioned probe of the present invention, skeleton structure is selected from：
Wherein, R1、R2And R3Separately from H, alkyl, unsaturated alkyl, miscellaneous alkyl, cycloalkyl, Heterocyclylalkyl, virtue
Chosen in base and heteroaryl；Y is O or Si.
In the above-mentioned probe of the present invention, R1、R2And R3It is substituted or unsubstituted, and independently selected from CnH2n+1、C10H7、
C12H9、OC6H5、OC10H7、OC12H9、CnH2nNOH、CnH2nCOOH、CnH2nNCS、CnH2nN3、CnH2nNH2、CnH2nSO3、CnH2nCl、
CnH2nBr、CnH2nI andWherein, n values are in 0 to 20；
R ' is from CnH2nNCS、CnH2nN3、CnH2nNH2、CnH2nCl、CnH2nBr、CnH2nI andMiddle selection.
In the above-mentioned probe of the present invention, probe m-TPE-RNS, i.e.,：
In the above-mentioned probe of the present invention, probe p-TPE-RNS, i.e.,：
In the above-mentioned probe of the present invention, probe is used to detect the trace Hg in water or active somatic cell2+。
In the above-mentioned probe of the present invention, probe is used to detect exogenous HClO or endogenous HClO, and thin for differentiating cancer
Born of the same parents and normal cell.
The present invention relates to a kind of across the key energy transfer of the dark-state just proposed (DTBET) mechanism and the mechanism high performance
Ratio metering type Hg2+Application in the development of probe and HClO sensors.To include more specifically, the invention particularly relates to one kind
The illuminator of tetraphenylethylene derivative with aggregation-induced emission (AIE) characteristic and as energy donor, wherein, rhodamine
Derivative is used as energy acceptor.Also, mechanism involved in the present invention can be applied to big pseudo- Stokes shift and
The research and development of the shiner of high s/n ratio, to contaminant trace species Hg2+Detection and endogenous HClO imaging in.
Brief description of the drawings
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing：
Fig. 1 shows p-TPE-RNS chemical formula；
Fig. 2 shows m-TPE-RNS chemical formula；
Fig. 3 shows the CH with different in moisture content310 μM of p-TPE-RNS (A) is in 355nm in CN- aqueous mixtures
The exciting of UV lamp under PL spectrum；
Fig. 4 shows the CH with different in moisture content310 μM of p-TPE-RNS (B) is in 485nm in CN- aqueous mixtures
The PL intensity distributions being under the exciting of 355nm UV lamp；
Fig. 5 shows the CH with different in moisture content310 μM of m-TPE-RNS (C) is in 355nm in CN- aqueous mixtures
The exciting of UV lamp under PL spectrum；
Fig. 6 shows the CH with different in moisture content310 μM of m-TPE-RNS (D) is in 480nm in CN- aqueous mixtures
The PL intensity distributions being under the exciting of 355nm UV lamp；
Fig. 7 is represented in the absence of 2 equivalent Hg2+(row 1 and row 2) and 2 equivalent Hg be present2+In the case of (row 3 and row 4)
With different in moisture content fw% CH310 μM of m-TPE-RNS is respectively in ambient light and 365nm UV lamp in CN- aqueous mixtures
Excite under photo；
Fig. 8 shows the Hg in different content2+In the presence of in CH310 μM in CN- aqueous mixtures (there is 60% moisture)
PL spectrum of the p-TPE-RNS (A) under 355nm the exciting of UV lamp；
Fig. 9 shows the Hg in different content2+In the presence of in CH310 μM in CN- aqueous mixtures (there is 60% moisture)
PL spectrum of the m-TPE-RNS (B) under 355nm the exciting of UV lamp；
Figure 10 is shown in different metal ions (1mM K+、Ca2+、Na+、Mg2+) in the presence of, in CH3CN- aqueous mixtures
10 μM of p-TPE-RNS (A) PL spectrum in (there is 60% moisture)；
Figure 11 is shown in the presence of other metal ions (20 μM), in CH3In CN- aqueous mixtures (there is 60% moisture)
10 μM of m-TPE-RNS (C) PL spectrum；
Figure 12 is shown in CH310 μM of p-TPE-RNS (B) PL intensity in CN- aqueous mixtures (there is 60% moisture)
Than (I595/I480) schematic diagram；Wherein, informal voucher represents：Different metal ions be present in blank；Secret note represents：With the gold of mark
Belong to ion processing, then add 20 μM of Hg2+；
Figure 13 is shown in CH310 μM of m-TPE-RNS (D) PL intensity in CN- aqueous mixtures (there is 60% moisture)
Than (I595/I480) schematic diagram；Wherein, informal voucher represents：Different metal ions be present in blank；Secret note represents：With the gold of mark
Belong to ion processing, then add 20 μM of Hg2+；
Figure 14 shows the Hg in 0-10ppb2+In the presence of, the CH with 70% moisture30.1 μM in CN- aqueous mixtures
M-TPE-RNS (A) fluorescence spectrum；
Figure 15 shows the Hg in 0-3ppb2+In the presence of, the Linear Fit Chart of the m-TPE-RNS (B) shown in Figure 14；
Figure 16 shows the Hg in 0-10ppb2+In the presence of, the CH with 70% moisture30.1 μM in CN- aqueous mixtures
P-TPE-RNS (C) fluorescence spectrum；
Figure 17 shows the Hg in 0-3ppb2+In the presence of, the Linear Fit Chart of the p-TPE-RNS (D) shown in Figure 16；
Figure 18 shows p (m)-TPE-RNS Hg2+The schematic diagram of sensing mechanism；
Figure 19 shows TPE chemical formula；
Figure 20 shows RNO chemical formula；
Figure 21 shows p-TPE-RNO chemical formula；
Figure 22 shows m-TPE-RNO chemical formula；
Figure 23 shows 10 μM TPE, RNO, m-TPE-RNO and p-TPE-RNO in CH3CN- water (v/v, 1：1) mixture
In absorption spectrum (A)；
Figure 24 is shown in CH3CN- water (v/v, 1：1) 10 μM RNO, m-TPE-RNO and p-TPE-RNO exist in mixture
530nm light excite under PL spectrum (B)；
Figure 25 is shown in CH3CN- water (v/v, 1：1) 10 μM TPE, RNO, m-TPE-RNO and p-TPE- in mixture
PL spectrum (C) of the RNO in the case where 355nm light excites；
Figure 26 shows that the PL of RNO, m-TPE-RNO and p-TPE-RNO at 595nm shown in Figure 24 and shown in Figure 25 is strong
Spend distribution map (D)；
Figure 27 has used the RNO optimized in theory molecular geometry and it is related to joint axis (black dash)
Donor transition dipole moment (arrow) calculating orientation line；
Figure 28 has used the p-TPE-RNO optimized in theory molecular geometry and itself and joint axis (the broken folding of black
Number) the calculating orientation line of related donor transition dipole moment (arrow)；
Figure 29 has used the m-TPE-RNO optimized in theory molecular geometry and itself and joint axis (the broken folding of black
Number) the calculating orientation line of related donor transition dipole moment (arrow)；
Figure 30 is shown determines evaluation figures of the p-TYPE-RNS to the toxicity of HeLa cells by MTT；
Figure 31 is shown in the absence of Hg2+(A-D) and 2 μM of Hg be present2+(E-H) have in the case of 30min by 20 μM
The fluorescence co-focusing micro-image of p-TPE-RNS dyeing 40min HeLa cells；Wherein, A, E are bright-field image；B, F is blueness
Channel image (420nm-520nm)；C, G is red channel image (550nm-650nm)；D, H is the R/B under 405nm light excites
Compare image；
Figure 32 shows the ClO in different content-In the presence of, 10 μM of p-TPE-RNS is in CH3CN- aqueous mixtures (have
60% moisture) in excited via 355nm light under PL spectrum；
Figure 33 shows ClOs of 10 μM of the p-TPE-RNS at 0-1.2 μM-In the range of linear fit curve map；
Figure 34 is shown comprising Cu2+, cysteine, Fe3+, glutathione, hydrogen peroxide, HOCl, KO2NO、·OH、
In CH in the presence of ROO, ROO and TBHP various biological analyte of interest (50 μM)3CN- aqueous mixtures (contain 60% moisture)
In 10 μM p-TPE-RNS PL intensity ratio (I590/I480) figure；
Figure 35 shows that p-TPE-RNS consecutive intervals under 355nm exciting are supervised in the presence of 50 μM of NaOCl
The PL intensity ratio (I of survey590/I480) schematic diagram；
Figure 36 shows the fluoroscopic image for the p-TPE-RNS that HeLa cells are handled via different modes；Wherein, A-C is
With the confocal images for the HeLa cells that 0.5h is incubated together with p-TPE-RNS；D-F pre-processes for (10 μM, 0.5h) with NaClO, so
The confocal images of 0.5h HeLa cells are incubated together with TPE-RNS afterwards；G-I is to be located in advance with 10 μM of NAC (HClO scavengers)
30min is managed, then incubates the confocal figure of the 30min cell by p-TPE-RNS dyeing together with 10 μM of NaClO at 37 DEG C
Picture；Wherein, A, D, G are blue channel image (420-530nm)；B, F, H are red channel image (570-680nm)；C, F, I are
The ratio image obtained by the fluorescence intensity ratio of red channel/blue channel；Meanwhile excitation wavelength 405nm；Engineer's scale is
20μm；P-TPE-RNS amount uses 5 μM；
Figure 37 shows the macrophage endogenous HOCl of live body RAW 264.7 fluoroscopic image；Wherein, A-C RAW
264.7 macrophages incubate 30min situation together with probe p-TPE-RNS；D-F is 1 μ g/ of the macrophages of RAW 264.7
mL-1LPS pretreatment 24h, and with 1 μ gmL-1PMA pre-processes 1h, and 30min feelings are then incubated together with probe p-TPE-RNS
Condition；G-I is 1 μ g/mL of the macrophages of RAW 264.7-1LPS pretreatment 24h, and with 1 μ gmL-1PMA pre-processes 1h, also uses
10 μM of NAC pretreatment 30min, 30min situation is then incubated together with probe p-TPE-RNS；Wherein, A, D, G are blueness
Channel image；B, F, H are red channel image (570nm-680nm)；C, F, I are covering blueness, red channel and bright-field image
Image；Meanwhile excitation wavelength 405nm；Engineer's scale is 20 μm；P-TPE-RNS amount uses 5 μM；
Figure 38 shows the fluoroscopic image of endogenous HOCl in the macrophages of live body RAW 264.7 caused by bacterium infection；
Wherein, A-C is the situation that the macrophages of RAW 264.7 incubate 30min together with probe p-TPE-RNS；D-F is RAW 264.7
Macrophage infects 4h in advance with Escherichia coli, and 30min situation is then incubated together with probe p-TPE-RNS；A, D is logical for blueness
Road image；B, F is red channel image (570-680nm)；C, F is the image of covering blueness, red channel and bright-field image；Together
When, excitation wavelength 405nm；Engineer's scale is 20 μm；P-TPE-RNS amount uses 5 μM；
Figure 39 shows endogenous HOCl in live body COS-7 and the HeLa cell that 30min is dyed by 10 μM of p-TPE-RNS
Fluoroscopic image；Wherein, A is bright-field image；B is the fluoroscopic image in the case where 510nm-550nm light excites；C is in 330nm-
385nm light excite under fluoroscopic image；Engineer's scale：30μm；
Figure 40 is endogenous HOCl in live body COS-7 and the MCF-7 cell for dyed 30min by 10 μM of p-TPE-RNS
Fluoroscopic image；Wherein, A is bright-field image；B is the fluoroscopic image in the case where 510nm-550nm light excites；Engineer's scale：30μm；
Figure 41 is the flow chart of m/p-TPE-RNS synthetic method；
Figure 42 is the flow chart of RNO synthetic method.
Embodiment
In one embodiment, Fig. 1 shows p-TPE-RNS chemical formula；Fig. 2 shows m-TPE-RNS chemistry
Formula.When moisture is 0%-50%, p-TPE-RNS PL intensity is at a fairly low, and assembles since when moisture is 55%；With
Strong emission peak centered on 485nm reaches maximum when moisture is 95%, as shown in Figure 3 and Figure 4.When moisture is less than 50%
When, m-TPE-RNS PL spectrum show similar weak PL signals；When moisture is higher than 55%, m-TPE-RNS PL spectrum are opened
Begin to assemble；But the PL intensity at 480nm reaches maximum when moisture is 60%, is dropped then as the increase of moisture
It is low, as shown in Figure 5 and Figure 6.The absolute quantum of p-TPE-RNS and m-TPE-RNS when moisture is 60% is determined using integration ball
Yield is respectively 4.1% and 15.2%.Moisture is from 0% to 60%, Hg2+Addition cause from blue-green to it is orange-red acutely it is glimmering
Light launches color change, as shown in Figure 7.Therefore, the moisture for selecting 60% is optimizing detection condition.
In one embodiment, with Hg2+The increase of concentration, the emissive porwer of the p-TPE-RNS at 485nm disappear,
New peak at 595nm dramatically increases.It is observed that obvious wait launch point at 564nm, and have greatly in the range of 110nm
Emission differences.I595/I485Intensity ratio from the absence of Hg2+In the case of 0.13 increase to exist 2 equivalent Hg2+'s
In the case of 462.9, here, ratio enhancer is more than 3500 times, as shown in Figure 8.In one embodiment, m-TPE-
RNS is to Hg2+Response and p-TPE-RNS to Hg2+Response it is similar, obvious wait at the red shift and 572nm at 115nm is launched
Point is it is observed that as shown in Figure 9.I595/I485Intensity ratio from the absence of Hg2+In the case of 0.17 increase in the presence of 2 work as
Measure Hg2+In the case of 1038.6, ratio enhancer is more than 6100 times here！Good detached peaks shows two kinds of stoichiometrics
Fluorescence probe is to Hg2+It is very sensitive.
The PL spectrum of DTBET systems in the presence of different metal ions are in the CH with 60% moisture3CN-H2O mixtures
In be collected into, as shown in Figure 10-Figure 13.For p-TPE-RNS, only there are 2 equivalent Hg in it2+In the case of just it is observed that
Obvious transmitting change from 485nm to 595nm, correspondingly, passes through other transition metal ions of 2 equivalents or 100 equivalents
K+、Ca2+、Na+、Mg2+The transmitting change triggered, which can ignore that, to be disregarded.In addition, in the presence of other metal ions, Hg2+
The I of initiation595/I485Intensity than sharply increase and be barely affected.M-TPE-RNS is in other metal ions to Hg2+Choosing
Selecting property is similar to p-TPE-RNS in other metal ions to Hg2+Selectivity.As a result show, even in other competitive gold
In the presence of belonging to ion, two kinds of DTBET systems all present the ratio metering type Hg with excellent selectivity2+Sense energy
Power.
The measurement of test limit：
Probe (0.1 μM) is dissolved in acetonitrile-water (3:7, volume：Volume) in mixed solution, measurement emission spectrum 10 times with
Determine background noise σ.It is then gradually increased Hg2+Concentration, by 0-10.0ppb, Hg is added every time2+Mixing collects fluorescence after 30 seconds
Spectrum.Then according to Hg2+Data of the concentration range from 0 to 3.0ppb, linear fitting obtain slope of a curve S.Accordingly, through meter
The test limit (3 σ/S) for drawing m-TPE-RNS and p-TPE-RNS is calculated, is identified as 0.3ppb and 1.2ppb.
For p-TPE-RNS, the detection limit value of two DTBET sensors is defined as 1.2ppb；For m-TPE-RNS, two
The detection limit value of individual DTBET sensors is defined as 0.3ppb, as shown in Figure 14-Figure 17, both less than the drink of U.S. EPA standard
With Hg in water2+Maximum acceptable concentration (2ppb).With the former Hg based on AIE mechanism2+Sensor is compared, DTBET sensors
Selectivity significantly improve.Hg2+Addition generate two influences：1) rhodamine core is produced；Due to there is fast and effectively TBET
Process, the generation of rhodamine core cause the PL intensity at 595nm to increase, and the PL intensity of TPE parts reduces；2) DTBET is reduced
The concentration of sensor, and the aggregation of sensor is reduced, so as to reduce further the PL intensity of TPE units.Therefore, DTBET
Hg2+Sensor shows outstanding ratio increment and low-down detection limit value.With reference to AIE and TBET mechanism, DTBET mechanism
It is probably the practical design strategy for developing high-performance sensors.
Ratio metering type Hg2+The working mechanism of sensor is summarized in figure 18.In no Hg2+In the case of, pass
Sensor is hydrophobic, and tends to assemble in aqueous.It is only poly- due to the non-emissive caprolactam form of rhodamine
The blue emission for closing TPE is expected.Use Hg2+After processing, the rhodamine fluorogen of positively charged can be produced, and improves it in water
Solubility.Therefore, because DTBET processes and non-radiative decay, TPE transmittings can not be observed, and the strong transmitting of rhodamine should
It is expected that.Therefore, ratio metering type Hg can be realized by this rational layout strategy2+Sensor.
Next, confirm the energy transfers of TPE derivatives (dark-state donor) to rhodamine portion by optical physics spectroscopy
Divide (acceptor), and the energy transfer efficiency (ETE) that p-TPE-RNS energy transfer efficiency (ETE) is 72%, m-TPE-RNS is
72%, as shown in Figure 19-Figure 26.Under solution state, the transmitting of donor set is not observed, up to 280nm big puppet
Stokes shift realizes, and this is beneficial to the bio-imaging with low background.
Theoretical calculation is carried out, to be best understood from the structure-property relationships of DTBET processes and DTBET boxes.p-TPE-RNO
The orientation of middle donor transition dipole moment and the angle that joint axis is in about 76.1 °, and donor transition dipole moment takes in m-TPE-RNO
To the inclination angle for joint axis being only in 29.2 °, as shown in Figure 27-Figure 29.When the transition dipole moment of donor is parallel to joint axis
Energy transfer rat is than the energy transfer rat when the transition dipole moment of donor is perpendicular to joint axis faster.Therefore, m-TPE-
The fact that RNO ETE speed should be faster than p-TPE-RNO, and this is higher than the ETE in p-TPE-RNO with the ETE in m-TPE-RNO
It is consistent.
Confocal fluorescent is imaged
In 5%CO2And under the conditions of 37 DEG C, by HeLa cells in the minimum essential medium MEM containing 10% hyclone
Culture.Using laser scanning co-focusing fluorescence carry out microcytoscope (Zeiss LSM7DUO) to HeLa cells carry out ratio into
Picture.Blue channel 420-520nm, red channel 550-650nm, excitation wavelength 405nm.Before imaging, delayed with phosphate
Rush salt solution (PBS, pH 7.4) solution washing cell three times.Scaled image is handled and obtained using image analysis program MATLAB.
The excellent Hg of DTBET boxes in the solution2+Sensing performance enables us to assess it in biological Hg2+In imaging
Potential application.Preferable solubility of the p-TPE-RNS due to its relatively large polarity and in water and more hold than m-TPE-RNS
Easily penetrate into active somatic cell.Meanwhile found when carrying out MTT measure, when p-TPE-RNS is at concentrations up to 100 μM, it is not observed
Obvious cytotoxicity, as shown in figure 30.Therefore, can be with HeLa cells using common focus point migration Laser Scanning Confocal Microscope
It is compared metering type Hg2+Imaging.In the absence of Hg2+In the case of 20min HeLa is dyed with 20 μM of p-TPE-RNS
Cell shows appropriate emissive porwer in blue channel (420-520nm), and in the red using only Blue Scale image
Weak fluorescence is shown in passage (550-650nm), this shows intracellular Hg2+It is horizontal very low, such as Figure 31 A- Figure 31 D institutes
Show.It is further incubated for 2 μM of Hg2+After 30min, it is observed that the intensity in blue channel is reduced, the intensity in red channel
It is remarkably reinforced, and scaled image is changed into orange from green, this shows Hg2+After incubation, intracellular Hg2+Level dramatically increases, and such as schemes
Shown in 31E- Figure 31 H.As a result, it was confirmed that p-TPE-RNS, which can be used as, is used for biological Hg2+The good ratio metering type imaging of detection
Agent.
Cell viability is tested：
Cell is seeded in 96 orifice plates with the density of every 5000 cells in hole.After overnight incubation, cultivate in each hole
Replaced with the fresh culture of the p-TPE-RNS containing various concentrations.After processing 24 hours, 10 microlitres of MTT solution are added per hole
(phosphate buffer 5mg/mL) solution).After being incubated 4 hours at 37 DEG C, 100 μ LSDS-HCl solution of addition (10%SDS,
0.01M HCl).After being incubated 6 hours at 37 DEG C, pass through Perkin-Elmer Victor3TMThe each concentration of instrument record is corresponding
570nm at absorbance.
In one embodiment, with ClO-The increase of concentration, emissive porwers of the p-TPE-RNS at 485nm are notable
Reduce, and the new peak at 595nm significantly increases.I595/I485Intensity ratio exist 5 equivalent Hg2+In the case of add
More than 120 times, as shown in figure 32.Separate well peak show that two kinds of stoichiometric fluorescence probes may be to HClO-Very
It is sensitive.P-TPE-RNS detection limit value is defined as 50nM, as shown in figure 33.NaClO addition can produce two effects：1) produce
Raw rhodamine core；Because fast and effectively TBET processes, the generation of rhodamine core cause the PL intensity at 595nm to increase, TPE portions
The PL intensity divided is reduced；2) reduce the concentration of sensor and reduce the aggregation of sensor, so as to further reduce the PL of TPE units
Intensity.Therefore, DTBET HClO sensors show outstanding ratio increment and low-down detection limit value.With reference to AIE and
TBET mechanism, DTBET mechanism are probably a kind of practical design strategy of the energy exploitation with the various sensors of high-performance.
The PL spectrum of DTBET systems in the presence of different living species are in the CH with 60% moisture3CN-H2O mixtures
In collected, as shown in figure 34.Only in the presence of 5 equivalent NaClO, it is observed that from 485nm to 595nm
Obvious transmitting change, correspondingly, passes through the other biological relative species of 5 equivalents or the Cu of 5 equivalents2+, cysteine, Fe3 +, glutathione, hydrogen peroxide, HOCl, KO2The transmitting change that NO, OH, ROO, ROO and TBHP are triggered can ignore that not
Meter.As a result show, two kinds of DTBET systems all have the ratio metering type HOCl sensing functions with excellent selectivity.p-
TPE-RNS is defined as 2min to HClO response time, and as shown in figure 35, this is compared with the HClO sensors that many has found
It hurry up.
In one embodiment, p-TPE-RNS is easily penetrated into living cells, therefore, is total to using common focus point migration
Focusing microscope can be compared exogenous HClO metering type imaging in HeLa cells.In the situation in the absence of NaClO
Under, the transmitting that 30min HeLa cells display appropriateness in blue channel (420-530nm) is dyed with 5 μM of p-TPE-RNS is strong
Degree, with hypofluorescence in the red channel (570-680nm) with weak scaled image, this shows intracellular with very
Low-level HClO, as shown in Figure 36 A-14C.When HeLa cells pre-process 30min with 10 μM of NaClO, then with 5 μM of p-
When TPE-RNS incubates 30min, it is observed that in blue channel in the reduction of emissive porwer and red channel emissive porwer it is bright
Aobvious enhancing, as shown in Figure 36 D-14F.Increased scaled image shows after NaClO is incubated, notable increasing horizontal intracellular HClO
Add.However, when HeLa cells pre-process 30min with 10 μM of NaClO and 10 μM of NAC (HClO scavengers), then with 5 μM
When p-TPE-RNS incubates 30min together, the intensity in red channel and scaled image reduces it is observed that as Figure 36 G- scheme
Shown in 36I.
In one embodiment, p-TPE-RNS promotes us to comment external source HClO good sensing performance in the solution
Estimate its potential application in endogenous HClO ratio metering type imaging.With 5 μM of p- in the case of in the absence of NaClO
The macrophages of RAW 264.7 of TPE-RNS dyeing medium emissive porwer of display in blue channel (420-530nm), in red
Display hypofluorescence in passage (570-680nm), this shows there was only very low-level HClO into the cell, such as Figure 37 A- Figure 37 C
It is shown.As 1 μ g/mL of the macrophages of RAW 264.7 LPS pretreatment 24h, and 1h, Ran Houyu are pre-processed with 1 μ g/mL PMA
When probe p-TPE-RNS incubates 30min together, it is observed that emissive porwer is reduced in blue channel, in red blood cell passage
Emissive porwer is remarkably reinforced, as shown in Figure 37 D- Figure 37 F；This shows after LPS and PMA are incubated and induced inflammation, intracellular HClO
Horizontal dramatically increases.However, as 1 μ g/mL of HeLa cells LPS pretreatment 24h, and 1h is pre-processed with 1 μ g/mL PMA,
30min also is pre-processed with 10 μM of NAC (HClO scavengers), 30min, Ke Yiguan are then incubated together with 5 μM of p-TPE-RNS
Observe, the emissive porwer in red channel and scaled image only has enhancing more by a small margin, as shown in Figure 37 G- Figure 37 I.These
As a result, it was confirmed that p-TPE-RNS can be for exogenous and endogenous HClO good ratio metering type preparation.
Next, we further test the ratio metering type imaging capability of endogenous HClO caused by bacterium infection.
The macrophages of RAW 264.7 are incubated into 30min together with 5 μM of p-TPE-RNS, it is observed that blue channel (420-
There is appropriate emissive porwer in 530nm), and can see the hypofluorescence in red channel (570-680nm), this shows cell
It is interior to have low-down HClO horizontal, as shown in Figure 38 A- Figure 38 C.However, when the macrophages of RAW 264.7 are pre- by Escherichia coli
4h is infected, when then carrying out incubation 30min with the p-TPE-RNS of 5 μM of probe, it is observed that emissive porwer in blue channel
Reduce and be remarkably reinforced with emissive porwer in red channel, such as Figure 38 D- such as Figure 38 F, this shows that coli-infection can promote cell
The horizontal significant increases of interior HClO.
It is reported that cancer cell can produce more active oxygens than normal cell.It is contemplated that can be with using p-TPE-RNS
Distinguish cancer cell and normal cell.Then we have co-cultured COS-7 cells (normal cell type) and HeLa cells (cancer cell),
And dyed with 10 μM of p-TPE-RNS, it is then possible to which it was observed that strong fluorescence corresponding with HeLa cells is strong in red channel
Degree, as shown in figure 39.When MCF-7 cells and normal COS-7 cells are co-cultured, it is observed that (cancer is thin with MCF-7 cells
Born of the same parents' type) similar high fluorescent pattern, as shown in figure 40.
Ultra-violet absorption spectrum is carried out on the array spectrophotometers of Milton Roy Spectronic 3000.Fluorescence spectrum
Recorded on the spectrometers of Perkin-Elmer LS 55.Quantum efficiency is measured in creek pine C11347Quantaurus-QY integrating spheres
Upper progress.High resolution mass spectrum obtains on the mass spectrographs of GCT Premier CAB 048.Nanometer aggregated particle size uses ZETA-
Plus potentiometric analyzers determine.
The invention also provides m/p-TPE-RNS and RNO synthetic method, as shown in Figure 41 and Figure 42.
P-RHZ synthesis：
Compound p-RBr (0.535g, 1.0mmol) is dissolved in 20mL ethanol, adds the hydrazine hydrates of 2mL mono-.Reaction is mixed
Thing flows back 6 hours under agitation, is then evaporated under reduced pressure and removes solvent.Residue purifies (n-hexane/acetic acid by silica gel chromatographic column
Ethyl ester, 5：1 to 3：1, volume/volume), obtain the p-RHZ (0.35g) of white powder, yield 64%；1H NMR(400MHz,
CDCl3):δ 7.82 (d, J=8.0Hz, 1H), 7.60 (dd, J=1.6Hz, J=8.0Hz, 1H), 7.26 (d, J=1.6Hz,
1H), 6.48 (d, J=8.8Hz, 2H), 6.44 (d, J=1.6Hz, 2H), 6.32 (dd, J=1.6Hz, J=8.8Hz, 2H),
3.62 (s, 2H), 3.37 (q, J=7.2Hz, 8H), 1.20 (t, J=7.2Hz, 12H)；13C NMR(100MHz,CDCl3):δ
165.3,153.8,153.3,149.1,131.7,128.8,128.0,127.2,124.6,108.1,103.6,98.0,65.8,
44.4,12.6；HRMS:Calculated value：[M+H]+535.1703, actual value：535.1729.
M-RHZ synthesis：
Synthesis program is similar with p-RHZ, using m-RBr as initiation material, yield, and 68%.1H NMR(400MHz,
CDCl3):δ 8.09 (d, J=2.0Hz, 1H), 7.59 (dd, J=1.0Hz, J=7.6Hz, 1H), 7.01 (d, J=7.6Hz,
1H), 6.47 (d, J=8.4Hz, 2H), 6.43 (d, J=2.4Hz, 2H), 6.32 (dd, J=2.4Hz, J=8.4Hz, 2H),
3.63 (s, 2H), 3.36 (q, J=7.2Hz, 8H), 1.19 (t, J=7.2Hz, 12H)；13C NMR(100MHz,CDCl3):δ
164.6,153.8,150.2,149.0,135.5,132.0,128.0,126.1,125.6,122.2,108.1,103.7,98.0,
66.0,44.4,12.6；HRMS:Calculated value：[M] 534.1630, actual value：534.1635.
The synthesis of p-TPE-RHZ compounds：
By p-RHZ (268mg, 0.5mmol), TPE-B (OH)2(188mg, 0.5mmol), Pd (PPh3)4(20mg,
0.017mmol) and K2CO3(138mg, 1.0mmol) is placed in the neck flasks of 100mL two.After vacuum nitrogen filling 3 times, 25mL is added
THF and 10mL H2O.By reactant mixture backflow overnight.THF solvents are removed under vacuo, with DCM and H2O liquid separations extract.Remove
After DCM, gained residue is purified by silica gel column chromatography (hexane/CH2Cl2/ ethyl acetate, 2:1:1, v/v/v) p-, is obtained
TPE-RHZ (324mg, 82%).1H NMR(400MHz,CDCl3):δ 7.95 (d, J=8.0Hz, 1H), 7.64 (dd, J=
1.6Hz, J=8.0Hz, 1H), 7.25 (d, J=1.6Hz, 1H), 6.98-7.07 (m, 19H), 6.49 (d, J=8.8Hz, 2H),
6.42 (d, J=2.4Hz, 2H), 6.30 (dd, J=2.4Hz, J=8.8Hz, 2H), 3.61 (s, 2H), 3.35 (q, J=6.8Hz,
8H), 1.17 (t, J=6.8Hz, 12H)；13C NMR(100MHz,CDCl3):δ166.0,153.8,152.2,148.9,
145.1,143.6,141.3,140.2,137.8,131.8,131.4,131.3,131.2,128.9,128.2,127.8,
127.7,127.6,127.0,126.6,126.5,123.3,122.1,108.1,104.5,97.9,66.1,44.4,12.6；
HRMS:Calculated value：[M] 786.3934, actual value：786.3986.
The synthesis of m-TPE-RHZ compounds：
Synthesis program is similar with p-TPE-RHZ, using m-RHZ as initiation material, yield, and 85%.1H NMR
(400MHz,CDCl3):δ 8.12 (d, J=2.4Hz, 1H), 7.65 (dd, J=2.4Hz, J=8.0Hz, 1H), 7.39 (d, J=
8.0Hz, 2H), 7.04-7.11 (m, 19H), 6.50 (d, J=8.8Hz, 2H), 6.43 (d, J=2.4Hz, 2H), 6.30 (dd, J
=2.4Hz, J=8.8Hz, 2H), 3.63 (s, 2H), 3.35 (q, J=6.8Hz, 8H), 1.17 (t, J=6.8Hz, 12H)；13C
NMR(100MHz,CDCl3):δ166.1,153.9,150.3,148.9,143.7,143.6,143.5,143.3,141.4,
141.0,140.4,137.9,131.9,131.4,131.3,131.2,130.6,128.2,127.8,127.7,127.6,
127.0,126.6,126.5,126.4,126.3,124.1,121.2,108.1,104.5,98.0,65.9,44.4,12.6；
HRMS:Calculated value：[M] 786.3934, actual value：786.3918.
P-TPE-RNS synthesis:
Isothiocyanic acid benzene methyl (135mg, 1.0mmol), p-TPE-RHZ (197mg, 0.25mmol) and triethylamine
(0.1mL) is dissolved in 10mL DMF, and under N2 protections, reactant mixture is stirred at room temperature 8 hours.It is removed in vacuum molten
Agent, gained residue purified by silica gel chromatographic column (hexane/CH2Cl2/ ethyl acetate, 2:1:1v/v/v), p-TPE- is obtained
RNS (210mg, 91%).1H NMR(400MHz,CDCl3):δ 8.02 (d, J=8.0Hz, 1H), 7.77 (dd, J=1.6Hz, J
=8.0Hz, 1H), 7.53 (s, 1H), 7.42 (d, J=1.6Hz, 1H), 7.30 (d, J=8.0Hz, 2H), 7.19 (t, J=
3.6Hz, 2H), 6.97-7.10 (m, 21H), 6.53 (d, J=8.8Hz, 2H), 6.45 (d, J=2.8Hz, 2H), 6.30 (dd, J
=2.8Hz, J=8.8Hz, 2H), 3.35 (q, J=6.8Hz, 8H), 1.17 (t, J=6.8Hz, 12H)；13C NMR(100MHz,
CDCl3):δ182.8,167.1,154.3,150.9,149.4,147.0,144.2,143.5,143.4,141.6,140.1,
137.7,137.3,132.0,131.4,131.3,128.3,127.9,127.7,127.6,126.6,126.5,126.1,
125.2,124.2,122.8,108.4,104.2,98.3,67.3,44.4,12.6；HRMS:Calculated value：[M] 921.4076, it is real
Actual value：921.4098.
The synthesis of m-TPE-RNS compounds：
Synthesis program is similar with p-TPE-RNS, using m-TPE-RHZ as initiation material, yield, and 92%.1H NMR
(400MHz,CDCl3):δ 8.20 (s, 1H), 7.85 (d, J=8.0Hz, 1H), 7.53 (s, 1H), 7.45 (d, J=8.0Hz,
2H), 7.31 (d, J=8.0Hz, 2H), 7.06-7.21 (m, 22H), 6.98 (s, 1H), 6.54 (d, J=8.8Hz, 2H), 6.47
(d, J=2.0Hz, 2H), 6.31 (dd, J=2.0Hz, J=8.8Hz, 2H), 3.36 (q, J=7.2Hz, 8H), 1.19 (t, J=
7.2Hz,12H)；13C NMR(100MHz,CDCl3):δ182.7,167.2,154.3,149.4,148.8,143.8,143.6,
143.5,142.0,141.6,140.2,137.7,137.3,133.0,132.1,131.4,131.3,131.2,129.7,
129.6,128.3,127.9,127.8,127.7,127.6,126.7,126.6,126.4,126.1,125.8,125.1,
125.0,124.2,121.9,108.4,104.2,98.4,67.2,44.4,12.6；HRMS:Calculated value：[M] 921.4076, it is real
Actual value：921.4036.
P-TPE-RNO synthesis：
Compound p-TPE-RNS (92mg, 0.1mmol) is dissolved in 5mLCH3In CN, HgCl is added2(54mg,
0.2mmol), mixture is stirred at room temperature 6 hours.After removing solvent, residue purifies (DCM/ by silica gel chromatographic column
MeOH, 20:1, v/v) p-TPE-RNO (80mg, 90%), is obtained.1H NMR(400MHz,CD2Cl2):δ11.20(br,1H),
8.30 (s, J=8.0Hz, 1H), 7.88 (d, J=8.4Hz, 1H), 7.73 (d, J=8.4Hz, 2H), 7.48 (s, 1H), 7.42
(d, J=8.0Hz, 2H), 7.02-7.21 (m, 21H), 6.89 (t, J=7.6Hz, 2H), 6.76-6.78 (m, 4H), 3.56 (q, J
=7.2Hz, 8H), 1.28 (t, J=7.2Hz, 12H)；13C NMR(100MHz,CDCl3):δ160.5,158.1,157.7,
156.0,155.6,144.4,143.6,143.5,143.4,142.1,141.8,140.1,139.0,136.3,132.0,
131.4,131.2,131.1,131.0,130.5,129.2,128.6,128.0,127.8,127.7,127.6,126.6,
126.2,122.2,121.7,117.7,114.1,113.9,96.3,46.0,12.3；HRMS:Calculated value：[M] 888.4272, it is real
Actual value：888.4253.
M-TPE-RNO synthesis：
Synthetic method is similar with p-TPE-RNO, using m-TPE-RNS as initiation material, yield 95%.1H NMR
(400MHz,CDCl3):δ 10.99 (br, 1H), 8.49 (s, 1H), 7.79 (d, J=8.0Hz, 1H), 7.73 (d, J=8.0Hz,
2H), 7.54 (d, J=8.0Hz, 2H), 7.27 (d, J=8.0Hz, 1H), 7.06-7.20 (m, 21H), 6.86 (t, J=7.2Hz,
1H), 6.79 (d, J=9.6Hz, 2H), 6.72 (s, 2H), 3.52 (q, J=6.8Hz, 8H), 1.28 (t, J=6.8Hz, 12H)；
13C NMR(100MHz,CDCl3):δ160.7,157.9,157.4,156.1,155.4,144.4,143.6,143.4,143.0,
141.6,140.3,138.8,136.2,132.2,131.5,131.4,131.3,131.2,130.9,128.6,128.5,
127.9,127.8,127.7,126.8,126.7,126.6,126.5,124.2,121.7,118.0,114.2,113.8,96.5,
46.1,12.7；HRMS:Calculated value：[M] 888.4272, actual value：888.4244.
It should be appreciated that for those of ordinary skills, can according to the above description be improved or converted,
And all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Claims (24)
1. a kind of ratio metering type probe with aggregation-induced emission characteristic, it is characterised in that the probe includes：
Wherein, each R is independently from H, alkyl, unsaturated alkyl, miscellaneous alkyl, cycloalkyl, Heterocyclylalkyl, aryl and heteroaryl
Choose；X is the chromophore being bonded with aggregation inducing transmitting fluorogen.
2. probe according to claim 1, it is characterised in that X is：
Wherein, each R is independently from H, alkyl, unsaturated alkyl, miscellaneous alkyl, cycloalkyl, Heterocyclylalkyl, aryl and heteroaryl
Choose；Y is O or Si；Z is that aggregation inducing launches fluorogen.
3. probe according to claim 2, it is characterised in that X is：
Wherein, Y is O or Si；Z is that aggregation inducing launches fluorogen.
4. probe according to claim 3, it is characterised in that the probe is：
Wherein, R1、R2And R3Separately from H, alkyl, unsaturated alkyl, miscellaneous alkyl, cycloalkyl, Heterocyclylalkyl, aryl and
Chosen in heteroaryl；Y is O or Si；Z is that aggregation inducing launches fluorogen.
5. probe according to claim 4, it is characterised in that R1、R2And R3It is substituted or unsubstituted, and independently
Selected from CnH2n+1、C10H7、C12H9、OC6H5、OC10H7、OC12H9、CnH2nNOH、CnH2nCOOH、CnH2nNCS、CnH2nN3、CnH2nNH2、
CnH2nSO3、CnH2nCl、CnH2nBr、CnH2nI andWherein, n values are in 0 to 20；
R ' is from CnH2nNCS、CnH2nN3、CnH2nNH2、CnH2nCl、CnH2nBr、CnH2nI andMiddle selection.
6. probe according to claim 4, it is characterised in that probe m-TPE-RNS, i.e.,：
7. probe according to claim 4, it is characterised in that probe p-TPE-RNS, i.e.,：
8. according to the probe described in claim 1-7 any one, it is characterised in that probe is used to detect in water or active somatic cell
Trace Hg2+。
9. according to the probe described in claim 1-7 any one, it is characterised in that probe is used to detect exogenous HClO or interior
Source property HClO, and for differentiating cancer cell and normal cell.
10. a kind of preparation method of probe, it is characterised in that comprise the following steps：
Step S1, p-RBr is dissolved in ethanol, adds a hydrazine hydrate, reaction generation p-RHZ；
Step S2, by p-RHZ, TPE-B (OH)2、Pd(PPh3)4And K2CO3Mixing, then THF and H is added in a nitrogen atmosphere2O,
Reaction generation p-TPE-RHZ；
Step S3, p-TPE-RHZ, isothiocyanic acid benzene methyl and triethylamine are mixed, in a nitrogen atmosphere reaction generation p-TPE-
RNS；
Wherein, p-RBr chemical formula is：
P-RHZ chemical formula is：
P-TPE-RHZ chemical formula is：
P-TPE-RNS chemical formula is：
11. preparation method according to claim 10, it is characterised in that in step sl, p-RBr is dissolved in ethanol, then
After adding a hydrazine hydrate, by stirring, flowing back, being evaporated under reduced pressure and remove solvent；Remove the residue after solvent and pass through silica gel chromatograph
Post purifies, so as to obtain p-RHZ.
12. preparation method according to claim 10, it is characterised in that step S2 includes：
By p-RHZ, TPE-B (OH)2、Pd(PPh3)4And K2CO3It is placed in one or two neck flask；Two neck flasks are vacuumized and are filled with
Nitrogen, then add THF and H2O, flowed back；
THF is removed under vacuo again, then with DCM and H2O carries out liquid separation extraction；DCM is removed to extract, then by after removing DCM
Residue purified by silica gel column chromatography, so as to obtain p-TPE-RHZ.
13. preparation method according to claim 10, it is characterised in that step S3 includes：
P-TPE-RHZ, isothiocyanic acid benzene methyl and triethylamine are dissolved in DMF, and stirred in a nitrogen atmosphere, then through vacuum
Remove solvent；Remove the residue obtained after solvent to purify by silica gel chromatographic column, so as to obtain p-TPE-RNS.
14. a kind of preparation method of probe, it is characterised in that comprise the following steps：
Step S1, m-RBr is dissolved in ethanol, adds a hydrazine hydrate, reaction generation m-RHZ；
Step S2, by m-RHZ, TPE-B (OH)2、Pd(PPh3)4And K2CO3Mixing, then THF and H is added in a nitrogen atmosphere2O,
Reaction generation m-TPE-RHZ；
Step S3, m-TPE-RHZ, isothiocyanic acid benzene methyl and triethylamine are mixed, in a nitrogen atmosphere reaction generation m-TPE-
RNS；
Wherein, m-RBr chemical formula is：
M-RHZ chemical formula is：
M-TPE-RHZ chemical formula is：
M-TPE-RNS chemical formula is：
15. preparation method according to claim 14, it is characterised in that in step sl, m-RBr is dissolved in ethanol, then
After adding a hydrazine hydrate, by stirring, flowing back, being evaporated under reduced pressure and remove solvent；Remove the residue after solvent and pass through silica gel chromatograph
Post purifies, so as to obtain m-RHZ.
16. preparation method according to claim 14, it is characterised in that step S2 includes：
By m-RHZ, TPE-B (OH)2、Pd(PPh3)4And K2CO3It is placed in one or two neck flask；Two neck flasks are vacuumized and are filled with
Nitrogen, then add THF and H2O, flowed back；
THF is removed under vacuo again, then with DCM and H2O carries out liquid separation extraction；DCM is removed to extract, then by after removing DCM
Residue purified by silica gel column chromatography, so as to obtain m-TPE-RHZ.
17. preparation method according to claim 14, it is characterised in that step S3 includes：
M-TPE-RHZ, isothiocyanic acid benzene methyl and triethylamine are dissolved in DMF, and stirred in a nitrogen atmosphere, then through vacuum
Remove solvent；Remove the residue obtained after solvent to purify by silica gel chromatographic column, so as to obtain m-TPE-RNS.
A kind of 18. trace Hg in water or active somatic cell2+Detection method, it is characterised in that comprise the following steps：
Step S1, water sample or active somatic cell sample are dyed using the probe as described in claim 1-9 any one；
Step S2, the photoluminescence spectra of the water sample being colored or active somatic cell sample is made；And visited according to photoluminescence spectra
Survey trace Hg2+。
19. detection method according to claim 18, it is characterised in that probe is m-TPE-RNS or p-TPE-RNS；
Step S2 comprises the following steps：
Calculate 595nm in the photoluminescence spectra of the water sample that is colored or active somatic cell sample under 355nm the exciting of UV lamp
The ratio between photoluminescence intensity, i.e. PL intensity ratio under lower photoluminescence intensity and 480nm；
Hg is determined according to PL intensity ratio2+Concentration.
A kind of 20. trace Hg in active somatic cell2+Detection method, it is characterised in that comprise the following steps：
Step S1, active somatic cell sample is dyed using the probe as described in claim 1-9 any one；
Step S2, fluorescence co-focusing micrograph is made to the active somatic cell sample being colored using laser scanning co-focusing microscope
Picture；And trace Hg is detected according to fluorescence co-focusing micro-image2+。
A kind of 21. trace ClO in water or active somatic cell-Detection method, it is characterised in that comprise the following steps：
Step S1, water sample or active somatic cell sample are dyed using the probe as described in claim 1-9 any one；
Step S2, the photoluminescence spectra of the water sample being colored or active somatic cell sample is made；And visited according to photoluminescence spectra
Survey trace ClO-。
22. detection method according to claim 21, it is characterised in that probe p-TPE-RNS；
Step S2 comprises the following steps：
Calculate 595nm in the photoluminescence spectra of the water sample that is colored or active somatic cell sample under 355nm the exciting of UV lamp
The ratio between photoluminescence intensity, i.e. PL intensity ratio under lower photoluminescence intensity and 485nm；
ClO is determined according to PL intensity ratio-Concentration.
A kind of 23. trace ClO in active somatic cell-Detection method, it is characterised in that comprise the following steps：
Step S1, active somatic cell sample is dyed using the probe as described in claim 1-9 any one；
Step S2, fluorescence co-focusing is made to the active somatic cell sample being colored using common focus point migration Laser Scanning Confocal Microscope
Micro-image；And trace ClO is detected according to fluorescence co-focusing micro-image-。
24. the resolving method of a kind of cancer cell and normal cell, it is characterised in that comprise the following steps：
Step S1, biopsy sample is dyed using the probe as described in claim 1-9 any one；
Step S2, the fluoroscopic image for the biopsy sample that shooting is colored；The different fluorescence of cell according to fluoroscopic image are strong
Degree realizes the resolution to cancer cell and normal cell.
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