CN109705147A - A kind of environment sensitive dyestuff and its preparation method and application - Google Patents
A kind of environment sensitive dyestuff and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to fluorescent material technical fields, more particularly to a kind of fluorescent material with environment sensitive.The present invention provides a kind of environment sensitive dyestuff, and the structural formula of the environment sensitive dyestuff is shown in formula I, in Formulas I, A1And A2To contain the substance with supplied for electronic property group；R1、R2、R3And R4Selected from following group: alkyl, substituted benzene ring or substituted thiophene ring.Gained environment sensitive dye molecule of the invention has and all has the advantages that sensibility to microenvironment in solution state and state of aggregation, and furthermore in solution state, when being used as polar sensitive dyestuff, higher fluorescence quantum yield is all had in different solvents.
Description
Technical field
The present invention relates to fluorescent material technical fields, more particularly to a kind of fluorescent material with environment sensitive.
Background technique
The dyestuff of environment sensitive can change the variation of luminescent color or intensity response environment, such as polarity, pH and viscosity etc.
(also referred to as molten cause chromotropic dye).This characteristic makes them be widely used in fluorescence probe, chemical sensor, micro-environmental variation inspection
Survey, bio-imaging, molecular switch and the mutually fields such as separation visualization.
Environment sensitive dye molecule is mainly realized by forming Intramolecular electron transfer state.When dyestuff is excited by light
Afterwards, charge is transferred to acceptor groups from donor, generates the excitation state with high dipole moment.Then, excitation state by with solvent pairs
Extremely sub interaction and relax, therefore red shift occurs in polar solvent for its fluorescence peak, and corresponding color is moved to feux rouges direction
It is dynamic.In general, the requirement of environment sensitive dyestuff is: (1) having big Stokes shift to avoid self absorption effect；(2)
With the variation of environment, acute variation occurs for fluorescence color；(3) high luminescence generated by light quantum is all had in varying environment to produce
Rate.Usually there is distortion charge transfer state and the molecule of plane charge transfer state to be commonly used for environment sensitive dyestuff.With distortion
The molecule of charge transfer state has big Stokes shift and violent color change, but quantum yield in different environments
There is very big difference.Such as in polar solvent, quantum yield can significantly decay or even fluorescence disappears.Opposite, have
The molecule of plane charge transfer state all has higher quantum yield in varying environment, but its color change is not obvious enough.
In addition, the dye molecule of environment sensitive usually has the aromatic ring of conjugation.Such molecule can generate by force in state of aggregation
Intermolecular pi-pi accumulation interaction, cause its fluorescence to be quenched, such as solid environment measuring and phase structure can not be applied to
The fields such as visualization.Therefore, developing while having the luminescent dye molecule of solution and state of aggregation environment sensitive is to have extensively
Application prospect.
Summary of the invention
In view of the foregoing drawbacks, the environment sensitive dye molecule new technical problem to be solved by the invention is to provide one kind,
It has and all has the advantages that sensibility to microenvironment in solution state and state of aggregation, and furthermore in solution state, being used as, polarity is quick
When infection material, higher fluorescence quantum yield is all had in different solvents.
Technical solution of the present invention:
The invention solves first technical problem be to provide a kind of environment sensitive dyestuff (solvatochromic dyestuff),
Structural formula is shown in formula I:
Wherein, A1And A2To contain the substance with supplied for electronic property group；R1、R2、R3And R4It is identical independently of one another or
Different is selected from following group: alkyl, substituted benzene ring or substituted thiophene ring.
Further, in Formulas I, A1And A2For aromatic rings or substituted aroma ring；Further, the aromatic rings be selenophen,
Benzene, thiophene, furans, bithiophene, benzothiophene, benzene thiophene, naphthalene or anthracene；Substituent group on the substituted aroma ring be-F ,-
Cl、-Br、-I、-R、-OR、-SR、-NH2, at least one of-NHR or-NRR ', wherein it is 1 that R and R ', which is selected from carbon atom number,
~20 alkyl straight-chain or alkyl branches.
Further, A1For 2- bromine selenophen, A2For phenyl ring.
Further, R1、R2、R3And R4It chooses and compound is synthesized to hexyl benzene or compound is synthesized to methylbenzene.
The invention solves second technical problem be to provide the preparation method of above-mentioned environment sensitive dyestuff, shown preparation
Method are as follows: II compound represented of formula is dissolved in organic solvent, is added under bromo-succinimide or bromine room temperature and reacts
To brominated product；Brominated product is not required to purify, and is directly dissolved in organic solvent；Then oxidant progress oxidation reaction is added to obtain
Environment sensitive dyestuff shown in Formulas I.
Further, structural formula shown in Formula II is selected from one of following compounds:
Further, the oxidant is hydrogen peroxide, metachloroperbenzoic acid, peroxosulphuric hydrogen potassium complex salt or oxygen
Gas.
Further, the organic solvent is at least one of chloroform, methylene chloride, acetone or tetrahydrofuran.
Further, the above method includes the following steps:
(1) Formula II compound represented and bromo-succinimide or bromine are dissolved in organic solvent, it is protected from light 1~
5h (preferably 2h) adds water quenching reaction after reaction；Product is extracted, is washed, and organic phase is dried to obtain crude product, directly
Tap into row in next step；
(2) crude product obtained by step (1) is directly dissolved in organic solvent, and it is (excellent to add 0.5~4h of oxidant normal-temperature reaction
It is selected as 3h), after reaction, add water quenching reaction；It extracted, washed, obtained after organic phase is dry using column chromatography
Solid, that is, environment sensitive of the present invention dyestuff.
The invention solves third technical problem be to provide the application of above-mentioned environment sensitive dyestuff:
The environment sensitive dyestuff is detected for environment polarity and bio-imaging；Or:
The environment sensitive dyestuff is for polymer phase separation visualization detection neck field；Or:
The environment sensitive dyestuff is used as the intellectual material of pH response.
Dye molecule provided by the invention shows blue light in nonpolar n-hexane, with the continuous increasing of solvent polarity
Add, red shift gradually occurs for fluorescence, has molten cause discoloration, can be applied to the detection of environment polarity and bio-imaging.In addition, by
Still there is fluorescence when this molecule is in state of aggregation, and with the enhancing of polymer polarity red shift can occur for fluorescence, therefore it is available
Visualization field of detecting is separated in polymer phase.Further, since in this molecule, there are carboxyls, therefore its intelligence that can be used as pH response
Materials'use.
Beneficial effects of the present invention:
The present invention has synthesized a series of environmentally sensitive luminescent dye molecules, due to having very between its carbonyl and carboxyl
Strong intramolecular hydrogen bond, therefore molecule keeps plane conformation, and higher fluorescence quantum yield is all had in various solvents；Such as strong
Quantum yield in polar solvent acetonitrile is 10%, and quantum yield is 62% in chloroform.In addition, after molecule is excited,
The charge transfer state of generation causes carbonyl alkalinity to increase, it may occur that intermolecular proton transfer generates more stable excitation state；?
During this, the movement of negative electrical charge position causes the transition dipole moment of this molecule to change a lot；Therefore it is in a solvent
Fluorescence color generate very violent variation with polar variation.On the other hand, due to molecular side chain (R1、R2、R3And R4)
Play the role of that chromophore (conjugated main chain) is isolated, therefore it still has fluorescence generation in state of aggregation, and this fluorescence is to polymerization
Object polar sensitive.
To sum up, the luminescent dye molecule of present invention gained environment sensitive has the advantage that (1) is molten in opposed polarity
There is very violent color change in agent, and color is from blue to orange, basic covering visible light area；(2) in different solvents
All have be more than 10% high-fluorescence quantum yield, especially in chloroform, quantum yield reaches 62%；(3) in state of aggregation,
Such molecule still has fluorescent emission, and it changes with polymer polarity, can be used for polymer phase separation visual research.
Detailed description of the invention:
Fig. 1 is fluorescence emission spectrum of the ISOAA-H fluorescent molecule of the embodiment of the present invention 1 in opposed polarity solvent.
Fig. 2 is fluorescence photo of the ISOAA-H fluorescent molecule of the embodiment of the present invention 1 in opposed polarity solvent (in 365nm
It takes pictures under ultraviolet lamp).
The ISOAA-H fluorescent molecule that Fig. 3 is 1% is dispersed in fluorescence emission spectrum in different polymeric matrixs and pure
The fluorescence emission spectrum (excitation wavelength 365nm) of ISOAA-H powder.
The ISOAA-H fluorescent molecule that Fig. 4 is 1% is dispersed in the phase separation structure figure in different blend polymers.
Fig. 5 is fluorescence emission spectrum of the ISOAA-M fluorescent molecule of the embodiment of the present invention 3 in opposed polarity solvent.
Specific embodiment
The present invention provides a series of environmentally sensitive luminescent dye molecules, and structural formula is shown in formula I, has in Formulas I
There is the six-membered ring structure composed by carboxyl and carbonyl there are intramolecular hydrogen bond；A1And A2For the structure with supplied for electronic property；
R1、R2、R3And R4For the structure with certain steric hindrance；So that the molecule of the structural formula can be as environment sensitive dyestuff point
Son, having all has the advantages that sensibility to microenvironment in solution state and state of aggregation, furthermore in solution state, is being used as polarity
When sensitive dye, higher fluorescence quantum yield is all had in different solvents.This is mainly due to following reasons: (1) by
There is very strong intramolecular hydrogen bond between carbonyl and carboxyl in molecule, therefore molecule keeps planar conjugate (chromophore) conformation,
Therefore this molecule has fluorescent emission；Since this molecule is plane conformation, therefore higher fluorescence volume is all had in various solvents
Sub- yield；(2) after molecule is excited, charge can be from power supply subdivision A1And A2It is transferred to electrophilic carbonyl and carboxyl, is formed
Charge transfer state；Charge transfer state interacts in opposed polarity solvent with solvent dipole, will lead to its red shift that shines, produces
Raw different color；Formula I compound represented can be sent out since carboxyl and carbonyl are linked together by intramolecular hydrogen bond
Raw intermolecular proton transfer, generates more stable excitation state；In the process, transition dipole moment (the excitation state dipole of molecule
The difference of square and the ground state dipole moment) it will increase, therefore will lead to and generate violent color change (transition dipole in different solvents
Square is bigger, and molecule is more sensitive to solvent polarity, and color change is more obvious)；(3) for conjugated molecule, assembling
Generally fluorescent quenching can be led to due to strong pi-pi accumulation when state, the present invention in molecule due to steric hindrance side chain exist,
It will lead to chromophore and be in segregate state, pi-pi accumulation is suppressed, and unimolecule state is mainly presented in molecule, therefore in state of aggregation
When can also generate fluorescent emission；And unimolecule can generate dipole-dipole interaction with polymeric matrix, show to polymer
The polar responsiveness of matrix.
The synthetic reaction formula of the preparation method of environment sensitive dyestuff of the present invention is as follows:
The embodiments given below are intended to further illustrate the invention, but is not to be construed as to the scope of the present invention
Limitation, person skilled in art is all to be all belonged to the scope of the present invention based on the technology that the content of present invention is realized.
The synthesis of 1 ISOAA-H of embodiment
The synthetic route of environment sensitive fluorescent molecule ISOAA-H is as shown in formula III:
NBS is N- bromo-succinimide in reaction equation, and chloroform is chloroform, and oxone is multiple for peroxosulphuric hydrogen potassium
Close salt (K2SO4·KHSO4·KHSO5), NaHCO3For sodium bicarbonate, DCM is methylene chloride, and acetone is acetone, H2O is water,
R.T indicates room temperature；
Specific synthesis step is as follows:
(1) IDS (180mg, 0.200mmol, 1eq) and NBS (78.0mg, 0.440mmol, 2.2eq) are dissolved in 5.00mL
Among chloroform, it is protected from light 2h, after reaction, adds water quenching reaction；Product is extracted with dichloromethane, and is washed with water, organic
It is dry to be added to anhydrous sodium sulfate, obtains crude product and directly carries out in next step；
(2) by 8.00mL acetone, 10.0mL methylene chloride, 11.0mL water is made into mixed solution, and previous step crude product is dissolved in
Wherein, sodium bicarbonate (380mg) then is added, oxone (K2SO4·KHSO4·KHSO5) (701mg, 1.14mmol, 6eq), often
Temperature reaction 3h adds water quenching reaction after reaction；Extraction is washed three times with water and methylene chloride, organic phase anhydrous slufuric acid
Sodium is dry, and (solvent PE:DCM=1:1, product exist the column chromatography dressed up after being spin-dried for using 200-300 mesh silica gel
It is in glassy yellow fluorescence under 365 ultraviolet lamps)；Obtain yellow solid 41.0mg, yield 17.0%.
1H NMR(400MHz,CDCl3)δ14.62(s,1H),7.85(s,1H),7.25(s,1H),7.23(s,1H),7.09
(dd, J=22.7,3.6Hz, 16H), 6.35 (s, 1H), 2.57 (dd, J=15.9,8.9Hz, 8H), 1.59 (dd, J=14.5,
6.7Hz, 8H), 1.37-1.23 (m, 24H), 0.87 (dd, J=6.7,2.4Hz, 12H)13C NMR(100MHz,CDCl3)δ
195.24,165.12,161.93,159.86,155.75,153.83,150.12,143.42,142.76,142.59,141.16,
139.81,133.95,133.04,129.66,128.94,128.86,128.65,127.73,123.45,122.44,117.32,
64.70,61.59,35.68,35.62,31.84,31.44,31.40,29.85,29.23,22.73,14.24.HRMS(m/z):
[M]+,calcd for C64H73BrO3Se,1049.3981；found:1049.3964.
Fluorescence emission spectrum of the product I SOAA-H in different solvents of the embodiment and photo in the UV lamp are respectively such as
(concentration 10 shown in Fig. 1 and 2-5M, excitation wavelength 365nm)；It can be seen that the fluorescence emission peak of ISOAA-H from two figures
Wavelength continuous red shift with the enhancing of solvent polarity, shows obviously molten cause metachromatism；Corresponding color is from indigo plant
Color (n-hexane) gradually becomes orange (acetone and acetonitrile), basic covering visible light area.Its corresponding fluorescence quantum yield (Fig. 1
Shown in) it is all larger than 10%, maximum value 62% is reached in chloroform；Show that ISOAA-H is that a kind of pair of environment polarity is very sensitive
Dye molecule, and the sub- yield of higher amount can be kept in various solvents.
Embodiment 2
The present embodiment is that 1 gained molecule ISOAA-H of embodiment is dispersed in the preparation method in different polymer and blend,
Specific step is as follows:
(1) by polystyrene (PS), polymethyl methacrylate (PMMA), polyisoprene (PIP), styrene-fourth two
Alkene-styrene copolymer (SBS) and polyethylene glycol (PEG) are dissolved in good solvent respectively, and (PS, PMMA, SBS and PI are dissolved in
In toluene, PEG is dissolved in chloroform) it is configured to the solution of 50mg/ml；ISOAA-H is dissolved in toluene and is configured to 10mg/ml
Solution；
(2) 1% ISOAA-H is added separately in PS, PMMA, PI, SBS and PEG solution to (ISOAA-H is in polymer
In mass fraction be 1%), to stir 2 hours, be coated on quartz glass by drop-coating later, dried；Obtained sample
It is tested in Fluorescence Spectrometer respectively with pure ISOAA-H powder, excitation wavelength 365nm；Test results are shown in figure 3,
From figure 3, it can be seen that ISOAA-H powder shows fluorescent orange, the peak value 599nm of emission peak；In addition, with polymer
The polar of matrix is continuously increased, and red shift gradually occurs for the fluorescence peak of ISOAA-H in a polymer matrix, shows apparent pole
Property dependence；
(3) respectively by 1) PS and PI, 2) PS and SBS, 3) PMMA and PI be added in the mixing of 1:1 (mass ratio) ratio
1% ISOAA-H (mass fraction of the ISOAA-H in blend polymer is 1%), is stirred for 2h later and is uniformly mixed；
The blend polymer of configured doping 1%ISOAA-H is spin-coated on 1cm using the rate of 1000r/min in sol evenning machine2's
On sheet glass, imaging test is carried out on fluorescence microscope again later, exciting light is ultraviolet light；Test results are shown in figure 4, by scheming
4 it is found that three kinds of blends can express the different phase separation structure of color under fluorescence microscope, such as in PS/SBS blending
In object, color is that the phase structure of sapphirine is PS phase, and in addition a phase is SBS phase (skipper)；It can be seen that being blended in PS/SBS
In object (50:50wt%), PS phase is continuous phase, and SBS is discontinuous phase；In PS/PI and PMMA/PI blend, it can observe
To obviously island structure, the island PS (PMMA) Xiang Wei phase, PI is continuous marine facies；To prove, present invention gained
ISOAA-H can be used as a kind of efficient environment sensitive fluorescent probe molecule and be applied to the visual research of polymer phase separation.
The synthesis of 3 environment sensitive fluorescent molecule ISOAA-M of embodiment
ISOAA-M structural formula and synthetic route are as shown in formula IV:
BuLi is n-BuLi in reaction equation, and THF is tetrahydrofuran, and AcOH is glacial acetic acid, and octane is normal octane.
Specific synthesis step is as follows:
(1) in an argon atmosphere, at -78 DEG C, to the anhydrous tetrahydro furan of 4- toluene bromide (1.77g, 10.4mol)
N-BuLi (4.2mL, 2.5M hexane solution, 10.4mmol) is added dropwise in (30mL) solution dropwise, mixture is kept at -78 DEG C
1 hour, backward mixture in be added dropwise compound 1 THF (10mL) solution (1.0g, 2.07mmol), -78 DEG C keep 1 hour
Afterwards, it is to slowly warm up to room temperature, is stirred overnight, is then quenched with water；Then it pours the mixture into water and is extracted with dichloromethane,
Organic layer is dry with anhydrous sodium sulfate, solvent is then removed under vacuum, obtains yellow solid, is directly used in next step
Suddenly；
(2) yellow solid is added in normal octane (100mL) and the mixture of acetic acid (10ml), then under argon gas to mixed
It closes and the 2 drop concentrated sulfuric acids is added in object, make reaction reflux 3 hours and be quenched with water；Mixture is extracted with dichloromethane, and will be merged
Organic layer be washed with water three times, organic layer is dry with anhydrous sodium sulfate；After removing solvent, petroleum ether/methylene chloride is used
The mixture of (10:1) is purified by silica gel chromatography crude compound as eluent, obtain yellow solid IDS-M (398mg,
26.5%)；
1H NMR(400MHz,CDCl3) δ 7.87 (d, J=5.4Hz, 2H), 7.37 (s, 2H), 7.18 (d, J=5.4Hz,
2H), 7.13 (d, J=8.2Hz, 8H), 7.05 (d, J=8.2Hz, 8H), 2.30 (s, 12H) .HRMS (ESI) m/z:[M+Na]+,
calcd for C44H34Se2,745.0883；found,745.0858.
(3) IDS-M (318mg, 0.440mmol, 1eq) and NBS (172mg, 0.968mmol, 2.2eq) are dissolved in
Among 15.00mL chloroform, it is protected from light 2h, after reaction, adds water quenching reaction, product is extracted with dichloromethane, and is washed with water
It washs, organic anhydrous sodium sulfate that is added to is dry, obtains crude product and directly carries out in next step；
(4) by 8.00mL acetone, 10.0mL methylene chloride, 11.0mL water is made into mixed solution, and previous step crude product is dissolved in
Wherein, sodium bicarbonate (600mg) is added, oxone (K2SO4·KHSO4·KHSO5) (276mg, 0.449mmol, 1.5eq), often
Temperature reaction 3h adds water quenching reaction after reaction；Extraction is washed three times with water and methylene chloride.Organic phase anhydrous slufuric acid
Sodium is dry, and (solvent PE:DCM=1:1, product exist the column chromatography dressed up after being spin-dried for using 200-300 mesh silica gel
It is in glassy yellow fluorescence under 365 ultraviolet lamps)；Obtain yellow solid ISOAA-M 43.0mg, yield 18.2%.
1H NMR(400MHz,CDCl3, δ) and 14.55 (s, 1H), 7.84 (s, 1H), 7.24 (d, J=2.7Hz, 2H), 7.15-
7.02(m,16H),6.34(s,1H),2.34(s,6H),2.32(s,6H).13C NMR(100MHz,CDCl3,δ)164.88,
161.67,159.68,155.51,153.64,149.96,143.25,140.88,139.53,137.60,137.42,133.82,
132.88,129.52,129.43,129.37,128.48,127.57,123.47,122.21,117.05,64.49,61.36,
21.00,20.94.HRMS(ESI)m/z:[M+H]+,calcd for C44H33BrO3Se,769.0851；found,769.0899.
Fluorescence emission spectrum of the product I SOAA-M of the embodiment in different solvents (concentration 10 as shown in Figure 5-5M swashs
Hair wavelength be 365nm), from figure 5 it can be seen that the wavelength of the fluorescence emission peak of ISOAA-M with the enhancing of solvent polarity and
Continuous red shift shows obviously molten cause metachromatism, corresponding color and gradually becomes orange from blue, and basic covering can
Light-exposed area；Show that ISOAA-H is the very sensitive dye molecule of a kind of pair of environment polarity.
Claims (10)
1. a kind of environment sensitive dyestuff, which is characterized in that the structural formula of the environment sensitive dyestuff is shown in formula I:
Wherein, A1And A2To contain the substance with supplied for electronic property group；R1、R2、R3And R4Selected from following group: alkyl takes
For phenyl ring or substituted thiophene ring.
2. environment sensitive dyestuff according to claim 1, which is characterized in that the A1And A2For aromatic rings or replace virtue
Fragrant ring.
3. environment sensitive dyestuff according to claim 2, which is characterized in that the aromatic rings is selenophen, benzene, thiophene, furan
It mutters, bithiophene, benzothiophene, benzene thiophene, naphthalene or anthracene.
4. environment sensitive dyestuff according to claim 2 or 3, which is characterized in that the substituent group on the substituted aroma ring
For-F ,-Cl ,-Br ,-I ,-R ,-OR ,-SR ,-NH2, at least one of-NHR or-NRR ', wherein R and R ' is selected from carbon atom
The alkyl straight-chain or alkyl branches that number is 1~20.
5. the preparation method of the described in any item environment sensitive dyestuffs of Claims 1 to 4, which is characterized in that shown preparation method
Are as follows: Formula II compound represented is dissolved in organic solvent, reaction under bromo-succinimide or bromine room temperature is added and obtains bromine
Change product；Brominated product is not required to purify, and is directly dissolved in organic solvent；Then oxidant progress oxidation reaction is added and obtains Formulas I
Shown in environment sensitive dyestuff；
6. the preparation method of environment sensitive dyestuff according to claim 5, which is characterized in that the choosing of Formula II compound represented
From one of following compounds:
7. the preparation method of environment sensitive dyestuff according to claim 5 or 6, which is characterized in that the oxidant was
Hydrogen oxide, metachloroperbenzoic acid, peroxosulphuric hydrogen potassium complex salt or oxygen.
8. according to the preparation method of the described in any item environment sensitive dyestuffs of claim 5~7, which is characterized in that described organic
Solvent is at least one of chloroform, methylene chloride, acetone or tetrahydrofuran.
9. according to the preparation method of the described in any item environment sensitive dyestuffs of claim 5~8, which is characterized in that the preparation
Method includes the following steps:
(1) Formula II compound represented and bromo-succinimide or bromine are dissolved in organic solvent, are protected from light 1~5h,
After reaction, add water quenching reaction；Product is extracted, is washed, and organic phase is dried to obtain crude product, is directly carried out in next step；
(2) crude product obtained by step (1) is directly dissolved in organic solvent, adds oxidant 0.5~4h of normal-temperature reaction, reaction knot
Shu Hou adds water quenching reaction；It extracted, washed, the use of the solid that column chromatography obtains is the environment after organic phase is dry
Sensitive dye.
10. environment sensitive dyestuff is detected for environment polarity and bio-imaging；Or: for polymer phase separation visualization detection neck
Domain；Or: the intellectual material as pH response；Wherein, the environment sensitive dyestuff is the described in any item rings of Claims 1 to 4
Border sensitive dye；Or the dyestuff to be obtained using the described in any item preparation methods of Claims 1 to 4.
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|---|---|---|---|---|
| CN112321485A (en) * | 2019-08-05 | 2021-02-05 | 尚科纺织企业工业及贸易公司 | PH-sensitive dye for textile material, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104583267A (en) * | 2012-08-24 | 2015-04-29 | 默克专利股份有限公司 | Conjugated polymers |
| CN107814796A (en) * | 2017-10-16 | 2018-03-20 | 湖南大学 | A kind of environment sensitive dyestuff based on benzofuraxan and its preparation method and application |
-
2018
- 2018-12-25 CN CN201811586712.0A patent/CN109705147B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104583267A (en) * | 2012-08-24 | 2015-04-29 | 默克专利股份有限公司 | Conjugated polymers |
| CN107814796A (en) * | 2017-10-16 | 2018-03-20 | 湖南大学 | A kind of environment sensitive dyestuff based on benzofuraxan and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| ANDREY S. KLYMCHENKO: "Solvatochromic and Fluorogenic Dyes as Environment-Sensitive Probes: Design and Biological Applications", 《ACC. CHEM. RES.》 * |
| YANG, Z.等: "Macro-/Micro-Environment-Sensitive Chemosensing and Biological Imaging", 《CHEM. SOC. REV》 * |
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| CN112321485A (en) * | 2019-08-05 | 2021-02-05 | 尚科纺织企业工业及贸易公司 | PH-sensitive dye for textile material, preparation method and application thereof |
| CN112321485B (en) * | 2019-08-05 | 2024-03-08 | 尚科纺织企业工业及贸易公司 | PH-sensitive dye for textile material, preparation method and application thereof |
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