CN103992791A - Rhodamine-based pH value fluorescent probe with linear response in weak acid range and preparation method thereof - Google Patents
Rhodamine-based pH value fluorescent probe with linear response in weak acid range and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a rhodamine-based pH value fluorescent probe with linear response in weak acid range and a preparation method thereof. The rhodamine-based pH value fluorescent probe has a general formula (described in the specification), wherein R1, R2, R3 and R4 are hydrogens at the same time, or R1, R2, R3 and R4 can be one of hydrogen, C2-6 alkyl and C4-8 naphthenic base. Fluorescent response of the pH value fluorescent probe has good linearity in an interval of pH value of 5.0-7.0, and the linearity range can meet pH value detection requirement of most biological cells and organelles thereof; colour of the probe solution is changed to deep rose from no colour along with decrease of pH value, and the probe solution can be used for detection by naked eyes; the pH value fluorescent probe can selectively recognize hydrogen ions and is not interfered by other common positive ions; the pH value fluorescent probe has good sensitivity, and fluorescence quantum yield can be 0.599 when pH is 5.13.
Description
Technical field
The present invention relates to a kind of rhodamine base pH value fluorescent probe that has linear response in slightly acidic scope, particularly a kind of rhodamine base pH value fluorescent probe that has linear response in slightly acidic scope and preparation method thereof.
Background technology
PH value is the important parameter in the researchs such as physiology, pharmacology, pathology.PH in human body cell in much physiology, pathologic process, play an important role (Nature Rev. Mol. Cell. Biol., 2010,11 (1), 50-61).Acid or alkalescence is crossed and can be caused that by force cell function is disorderly, causes the heart, tuberculosis to become or neural class disease, when serious, even can be in peril of one's life.The variation of therefore monitoring intracellular ph value can provide important information for studying physiological and pathologic process.Measure pH value general by glass electrode, but due to exist the pH that electrochemistry is disturbed, the possible defects such as physical abuse are unsuitable for active somatic cell monitor (Cell Mol. Biol., 2000,46 (8), 1361-1374).Fluorescent probe detects Cellular pH value and belongs to noninvasive method, can not destroy sample, have simultaneously highly sensitive, selectivity good, instruments design is flexible, sample size is few, simple to operate, being applicable to the features such as high flux screening, is Perfected process (Trends in Analytical Chemistry, 2010 of detecting Cellular pH value, 29 (9), 1004-1013).
Generally in normal cell, there are two main pH value scopes: tenuigenin is mainly between 6.8-7.4, and the pH value of acid organoid is 4.5-6.0.For the pH value probe of these two scopes, had lot of documents report, and be respectively used to the qualitative examination of tenuigenin pH value and the detection of acid organoid (SCI, 2010,13 (6), 1148-1151).But for cancer cell, extremely the pH value that causes its cell due to the anaerobic metabolism by glycolytic pathway is than average low 0.55 unit of normal cell, the general scope (Bioorganic & Medicinal Chemistry Letters 22 (2012) 2440-2443) in 5.8-7.7 of its pH value.Take the existing bibliographical information of nuclear-magnetism, electrochemistry Method for cancer diagnostics that this abnormal pH value is target.Owing to having the pH value fluorescent probe of linear response less in this interval at present, so the rarely seen bibliographical information of Method for cancer diagnostics based on pH value fluorescent probe.Therefore developing a kind ofly has the pH value fluorescent probe of linear response to have great importance for cancer research and cancer diagnosis in slightly acidic scope (pH=5.0-7.0).The shortcomings such as in addition, the pH value fluorescent probe great majority of having developed at present exist sensitivity poor, and linearity range is narrower.Therefore developing a kind ofly has the pH value fluorescent probe of linear response to remain the study hotspot in this field in slightly acidic scope (pH=5.0-7.0).
Rhodamine is the dyestuff that contains xanthene structure, there is very high specific absorbance, long exciting and emission wavelength, higher fluorescence quantum yield and the good advantages such as light stability, as the parent of fluorescent probe a large amount of for building pH value fluorescent probe (Chem. Rev., 2012,112,1910-1956).While it is generally acknowledged that lactan structure when rhodamine base pH value probe is in five yuan of volution states, molar absorptivity and fluorescence quantum yield are very low, almost there is no fluorescence, when the carbonyl of rhodamine lactan is protonated, can cause the carbonnitrogen bond fracture in five yuan of volutions of probe, form open loop structure, fluorescence intensity significantly strengthens, thereby realizes the selective response of pH value (Org. Biomol. Chem., 2014,12,526-533).Lin Weiying etc. study discovery to this recognition mechanism, by regulate the ring strain of five yuan of volutions of rhodamine can regulate and control the response of rhodamine probe interval (Org. Biomol. Chem., 2011,9,1723-1726).The present invention adopts the group of large steric hindrance to regulate the response of rhodamine pH value probe interval according to this principle, has built a kind of rhodamine base pH value fluorescent probe that has linear response in slightly acidic scope (pH=5.0-7.0).
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of rhodamine base pH value fluorescent probe that has linear response in slightly acidic scope and preparation method thereof, fluorescent probe prepared by the method makes the open loop of rhodamine generation volution by hydrionic complexing induction, make the enhancing of probe molecule generation colour-change (colourless to deeply rose-colored) and fluorescent signal, the colour-change before and after its identification can be observed by bore hole.This probe has high selectivity to hydrogen ion, and other common ions are all without obviously disturbing, and the fluorescent signal of probe can produce linear response in the scope of pH=5.0-7.0, has the application prospect that detects pH value in biomass cells.
One of object of the present invention is to provide a kind of rhodamine base pH value fluorescent probe that has linear response in slightly acidic scope, and its structural formula is as follows:
Wherein: R
1, R
2, R
3, R
4hydrogen, or R simultaneously
1, R
2, R
3or R
4be selected from a kind of in hydrogen, a 2-6 carbon atom alkyl or 4-8 carbon atom cycloalkyl.
Two of object of the present invention is to provide a kind of preparation method who has the rhodamine base pH value fluorescent probe of linear response in slightly acidic scope.The method comprises the following steps:
(1) by dye stuff of rhodamine kinds and phosphorus oxychloride mol ratio, be that 1:2-5 takes dye stuff of rhodamine kinds and is dissolved in dry organic solvent, more slowly add the phosphorus oxychloride of proportional quantity, be warming up to back flow reaction, after reaction finishes, be down to room temperature and form reaction solution;
(2) by 2,6-diisopropyl aniline and acid binding agent mol ratio are that 1:10-30 takes 2,6-diisopropyl aniline, acid binding agent are dissolved in dry organic solvent and make solution, this solution is dropwise added in the formed reaction solution of step (1), be warming up to back flow reaction, after reaction finishes, use NaHCO
3solution washing, collected organic layer, anhydrous magnesium sulfate drying, suction filtration, removes solvent under reduced pressure, and column chromatography for separation obtains target compound.
In described step, organic solvent can be this area routine, preferably has a kind of 1,2-ethylene dichloride, acetonitrile, methylene dichloride, dimethyl sulfoxide (DMSO), chloroform, DMF or tetrahydrofuran (THF) of being selected from least.
In described step (2), acid binding agent adopts this area routine, the preferred pyridine of acid binding agent or triethylamine.
In described step (2), column chromatography filler used can be this area routine, is preferably aluminum oxide, and eluent can be this area routine, the methylene dichloride that preferred volume ratio is 20:1 and ethanol.
Specifically, the preparation method who has the rhodamine base pH value fluorescent probe of linear response in slightly acidic scope of the present invention, comprises the following steps:
1. 1 mole of dye stuff of rhodamine kinds is dissolved in dry organic solvent, more slowly adds 2-5 mole of phosphorus oxychloride, be warming up to backflow.After stirring reaction 4-6h, be down to room temperature.
2. 1 mole of 2,6-DIPA, 10-30 mole acid binding agent are dissolved in dry organic solvent, this solution is dropwise added in above-mentioned reaction system, be warming up to backflow, reaction 3-7h.Reaction finishes the rear 0.1M of using NaHCO
3solution washing, collected organic layer, anhydrous magnesium sulfate drying.Suction filtration, removes solvent under reduced pressure, and column chromatography for separation obtains target compound.
In described step, organic solvent is 1,2-ethylene dichloride, acetonitrile, methylene dichloride, dimethyl sulfoxide (DMSO), chloroform, DMF, tetrahydrofuran (THF), or their mixture.
In described step 2, acid binding agent is pyridine or triethylamine.
In described step 2, column chromatography filler used is aluminum oxide, and eluent is that volume ratio is methylene dichloride and the ethanol of 20:1.
The present invention has the building-up reactions formula of the rhodamine base pH value fluorescent probe of linear response to be in slightly acidic scope:
PH value fluorescent probe of the present invention is in neutral, alkaline system, and 540-660nm place does not have emission peak, illustrate this probe within the scope of this pH in five yuan of volution states.Along with the reduction of pH value, probe occurs that at 595nm place emission peak and fluorescence intensity strengthen gradually.Ultra-violet absorption spectrum variation tendency is consistent with fluorescence spectrum, and solution becomes deeply rose-coloredly from colourless, shows can observe the response of probe to pH value under bore hole condition.Probe is that 5.0-7.0 interval has good linearity at pH.The fluorescence quantum yield of probe when pH=5.13 can reach 0.599.According to Henderson-Hasselbach type equation: (log[(I
max-I)/(I-I
min)]=pKa-pH, the pKa that calculates probe is 5.826.This probe is expected to detect for the pH value of biomass cells, the especially research of cancer and diagnosis.
The invention has the beneficial effects as follows: the fluorescence response of pH value fluorescent probe of the present invention has good linearity in pH=5.0-7.0 interval, this linearity range can meet the requirement to most of biomass cellss and the detection of organoid pH value thereof.This probe solution, along with the color that reduces of pH value becomes deeply rose-coloredly from colourless, can be used for open hole detection.This probe energy selectivity is identified hydrogen ion, and is not subject to the interference of other Common Cations.This probe sensitivity is good, and the fluorescence quantum yield when pH=5.13 can reach 0.599.This probe is expected to detect for the pH value of biomass cells, the especially research of cancer and diagnosis.
Accompanying drawing explanation
Fig. 1 is the fluorescence emission spectrogram of fluorescent probe under condition of different pH in the embodiment of the present invention 1.Concentration and probe concentration is 50 μ M, and X-coordinate is wavelength (nm), and ordinate zou is fluorescence intensity, and excitation wavelength is 520nm.
Fig. 2 be in the embodiment of the present invention 1 fluorescent probe in the fluorescence intensity at 595nm place with pH value change curve.(the little figure in the upper right corner: at the linear relationship chart of fluorescence intensity and the pH value at 595nm place).Concentration and probe concentration is 50 μ M, and X-coordinate is wavelength (nm), and ordinate zou is fluorescence intensity, and excitation wavelength is 520nm.
Fig. 3 is the colour-change figure of fluorescent probe in different pH buffered soln in the embodiment of the present invention 1.PH value is from left to right followed successively by 2.0,3.0,3.5,4.0,4.5,5.0,5.2,5.5,5.8,6.0,6.5,7.0,8.0,9.0.
Fig. 4 is the fluorescence emission spectrum of fluorescent probe when pH=2.95 and the fluorescence emission spectrogram while coexisting with different metal ion (10mM) in the buffered soln of pH=7.4 in the embodiment of the present invention 1.Concentration and probe concentration is 50 μ M, and ionic concn is 10mM, and X-coordinate is wavelength (nm), and ordinate zou is fluorescence intensity, and excitation wavelength is 520nm.
Fig. 5 is fluorescence emission spectrogram when fluorescent probe coexists with different metal ion (10mM) in the buffered soln of pH=3.0 in the embodiment of the present invention 1.Concentration and probe concentration is 50 μ M, and ionic concn is 10mM, and X-coordinate is wavelength (nm), and ordinate zou is fluorescence intensity, and excitation wavelength is 520nm, (because there is figure, please write an embodiment).
Embodiment
Embodiment 1
(1) by 0.2395g(0.5mmol) rhodamine B be dissolved in 15mL dry 1,2-ethylene dichloride, slowly adds 0.15mL(1.6mmol) POCl
3, being warmed up to 83 ℃, back flow reaction 5h, is cooled to room temperature.
(2) by 0.1314g(0.6mmol) 2,6-DIPA, 2mL(14.3mmol) triethylamine is dissolved in 10mL1, in 2-ethylene dichloride, this solution dropwise added in above-mentioned steps (1) reaction system, is warmed up to 83 ℃, back flow reaction 5h.Reaction finishes the rear 0.1M of using NaHCO
3solution (3 * 20mL) washing, collected organic layer, anhydrous magnesium sulfate drying.Suction filtration, removes solvent under reduced pressure, and the neutral alumina of take carries out column chromatography (V as filler
methylene dichloride: V
methyl alcohol=20:1) obtain target compound 0.25g, yield 83.17%.m.p：305℃。
1HNMR?(400?MHz,?CDCl
3)?δ（ppm）=8.08?(dd,?J=6.8,?1.5?Hz,?1H),?7.70-7.60?(m,?2H),?7.36-7.27?(m,?2H),?7.00?(d,?J=7.7?Hz,?2H),?6.57?(d,?J=8.8?Hz,?2H),?6.31?(dd,?J=8.9,?2.6?Hz,?2H),?6.22?(d,?J=2.6?Hz,?2H),?3.31?(q,?J=7.0?Hz,?8H),?2.43?(dt,?J=13.4,?6.7?Hz,?2H),?1.13?(t,?J=7.0?Hz,?12H),?0.92?(d,?J=6.7?Hz,?6H),?0.47?(t,?J=8.4?Hz,?6H)；
13CNMR?(100?MHz,?CDCl
3)?δ（ppm）=167.35?(s),?156.57?(s),?149.71?(s),?149.48?(s),?148.72?(s),?133.18?(s),?131.99?(s),?130.36?(s),?129.56?(s),?128.85?(s),?128.49?(s),?125.07?(s),?123.71?(s),?123.15?(s),?108.94?(s),?107.60?(s),?98.48?(s),?77.34?(s),?76.91?(d,?J=23.1?Hz),?76.71?(s),?69.94?(s),?44.44?(s),?29.67?(s),?26.71?(s),?21.88?(s),?12.62?(s)；HRMS：anal.?calcd?for?C
40H
47N
3O
2：601.82；found：602.3762?(M+H
+)；IR(KBr，cm
-1)：2961.46，2926.15，2862.00，1687.00，1615.05，1515.56，1465.77，1353.88，1266.48，1220.38，1118.04，1014.60，785.91，761.03，702.14，543.67.
Embodiment 2
(1) by 0.1684g(0.5mmol) rhodamine 110 be dissolved in 15mL dry 1,2-ethylene dichloride, slowly adds 0.15mL(1.6mmol) POCl
3, being warmed up to 83 ℃, back flow reaction 5h, is cooled to room temperature.
(2) by 0.1314g(0.6mmol) 2,6-DIPA, 2mL(14.3mmol) triethylamine is dissolved in 10mL1, in 2-ethylene dichloride, this solution dropwise added in above-mentioned steps (1) reaction system, is warmed up to 83 ℃, back flow reaction 5h.Reaction finishes the rear 0.1M of using NaHCO
3solution (3 * 20mL) washing, collected organic layer, anhydrous magnesium sulfate drying.Suction filtration, removes solvent under reduced pressure, and the neutral alumina of take carries out column chromatography (V as filler
methylene dichloride: V
methyl alcohol=20:1) obtain target compound 0.17g.
Embodiment 3
(1) by 0.2395g(0.5mmol) rhodamine B be dissolved in 15mL dry 1,2-ethylene dichloride, slowly adds 0.15mL(1.6mmol) POCl
3, being warmed up to 83 ℃, back flow reaction 5h, is cooled to room temperature.
(2) by 0.1314g(0.6mmol) 2,6-DIPA, 1.15mL(14.3mmol) pyridine is dissolved in 10mL1, in 2-ethylene dichloride, this solution dropwise added in above-mentioned steps (1) reaction system, is warmed up to 83 ℃, back flow reaction 5h.Reaction finishes the rear 0.1M of using NaHCO
3solution (3 * 20mL) washing, collected organic layer, anhydrous magnesium sulfate drying.Suction filtration, removes solvent under reduced pressure, and the neutral alumina of take carries out column chromatography (V as filler
methylene dichloride: V
methyl alcohol=20:1) obtain target compound 0.23g.
Embodiment 4
(1) by 0.1684g(0.5mmol) rhodamine 110 is dissolved in the acetonitrile that 15mL is dry, slowly adds 0.15mL(1.6mmol) POCl
3, being warmed up to 80 ℃, back flow reaction 5h, is cooled to room temperature.
(2) by 0.1314g(0.6mmol) 2,6-DIPA, 2mL(14.3mmol) triethylamine is dissolved in 10mL acetonitrile, and this solution is dropwise added in above-mentioned steps (1) reaction system, is warmed up to 80 ℃, back flow reaction 5h.Reaction finishes the rear 0.1M of using NaHCO
3solution (3 * 20mL) washing, collected organic layer, anhydrous magnesium sulfate drying.Suction filtration, removes solvent under reduced pressure, and the neutral alumina of take carries out column chromatography (V as filler
methylene dichloride: V
methyl alcohol=20:1) obtain target compound 0.16g.
Embodiment 5
With fluorescent probe in the embodiment of the present invention 1, under condition of different pH, test fluorescence emission spectrum with the changing conditions of pH value.Fig. 1 is that the concentration in different pH values is the fluorescence spectrum figure of ethanol/water (v/v, 1:1, the pH=7.0) solution of the fluorescent probe that makes of the embodiment 1 of 50 μ M.Fluorescence exciting wavelength is 520nm.As we can see from the figure, in neutral, basic solution scope, this probe does not have emission peak at 540-700nm place, illustrate this probe within the scope of this pH in spirane structure.Along with the reduction of pH value, probe occurs that at 595nm place emission peak and fluorescence intensity strengthen gradually, but when pH value is less than 5.13 after, fluorescence intensity is decline to some extent again.Take rhodamine B as benchmark (Φ=0.89), according to data in figure, calculate, during pH=5.13, the fluorescence quantum yield of this probe is 0.599.
Embodiment 6
With fluorescent probe in the embodiment of the present invention 1, under condition of different pH, test the linear relationship of fluorescent emission intensity and pH value.Fig. 2 be the concentration in different pH values be ethanol/water (v/v, 1:1, the pH=7.0) solution of the fluorescent probe that makes of the embodiment 1 of 50 μ M in the fluorescence intensity at 595nm place with pH value change curve.Fluorescence exciting wavelength is 520nm.As we can see from the figure, at pH, be that 5.0-7.0 interval has good linear relationship.According to data in figure, according to Henderson-Hasselbach type equation (log[(I
max-I)/(I-I
min)]=pKa-pH, the pKa that calculates this probe is 5.826.
Embodiment 7
Experiment develops the color in different pH damping fluids with fluorescent probe in the embodiment of the present invention 1.Fig. 3 is that concentration is the different pH value buffered soln of the fluorescent probe that makes of the embodiment 1 of 50 μ M, pH value is from left to right followed successively by 2.0,3.0,3.5,4.0,4.5,5.0,5.2,5.5,5.8,6.0,6.5,7.0,8.0,9.0, places the photo after 20 minutes.As can be seen from the figure, this probe is along with pH value reduces, probe solution gradually and from colourless become deeply rose-colored.Show that probe can indicate the acidity change of tested systems under bore hole condition.
Embodiment 8
The fluorescent probe making with the embodiment of the present invention 1 carries out hydrionic selectivity experiment.Fig. 4 be concentration be in the embodiment of the present invention 1 of 50 μ M fluorescent probe when pH=2.95, and the fluorescence emission spectrogram while coexisting with different metal ion (10mM) in the buffered soln of pH=7.4.Fluorescence exciting wavelength is 520nm.As we can see from the figure, the K that adds 10mM in the fluorescent probe solution making to embodiment 1
+, Na
+, Ca
2+, Mg
2+, Al
3+, Fe
3+, Cu
2+, Ni
2+, Co
2+, Mn
2+, Sn
2+, Zn
2+during Deng metal ion, fluorescence spectrum between 550-750nm without emission peak.But when pH=2.95, the fluorescence spectrum of this probe obviously strengthens in 595nm place fluorescence intensity, there is a new emission peak.This illustrates that this probe has good selectivity to hydrogen ion.
Embodiment 9
The fluorescent probe making with the embodiment of the present invention 1 carries out anti-interference experiment.Fig. 5 be in the embodiment of the present invention 1 fluorescent probe in the buffered soln of pH=3.0 with K
+, Na
+, Ca
2+, Mg
2+, Al
3+, Fe
3+, Cu
2+, Ni
2+, Co
2+, Mn
2+, Sn
2+, Zn
2+fluorescence emission spectrogram when different metal ion (10mM) coexists.The concentration and probe concentration of experiment is 50 μ M, and excitation wavelength is 520nm.As we can see from the figure, various common metal ion K
+, Na
+, Ca
2+, Mg
2+, Al
3+, Fe
3+, Cu
2+, Ni
2+, Co
2+, Mn
2+, Sn
2+, Zn
2+existence very little or almost do not disturb to the interference of the pH response of this probe.Illustrate that probe has good freedom from jamming to common metal ion.
Although embodiment of the present invention are open as above, but it is not restricted to listed utilization in specification sheets and embodiment, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other modification, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details and illustrates here and the legend of describing.
Claims (8)
1. in slightly acidic scope, there is a rhodamine base pH value fluorescent probe for linear response, it is characterized in that this kind of fluorescent probe has following general structure:
Wherein: R
1, R
2, R
3, R
4adopt hydrogen simultaneously, or R
1, R
2, R
3or R
4be selected from a kind of in hydrogen, a 2-6 carbon atom alkyl or 4-8 carbon atom cycloalkyl.
2. in slightly acidic scope, there is a preparation method for the rhodamine base pH value fluorescent probe of linear response, it is characterized in that comprising the following steps:
(1) by dye stuff of rhodamine kinds and phosphorus oxychloride mol ratio, be that 1:2-5 takes dye stuff of rhodamine kinds and is dissolved in dry organic solvent, more slowly add the phosphorus oxychloride of proportional quantity, be warming up to back flow reaction, after reaction finishes, be down to room temperature and form reaction solution;
(2) by 2,6-diisopropyl aniline and acid binding agent mol ratio are that 1:10-30 takes 2,6-diisopropyl aniline, acid binding agent are dissolved in dry organic solvent and make solution, this solution is dropwise added in the formed reaction solution of step (1), be warming up to back flow reaction, after reaction finishes, use NaHCO
3solution washing, collected organic layer, anhydrous magnesium sulfate drying, suction filtration, removes solvent under reduced pressure, and column chromatography for separation obtains target compound.
3. a kind of preparation method who has the rhodamine base pH value fluorescent probe of linear response in slightly acidic scope according to claim 2, it is characterized in that in described step that organic solvent has at least is a kind ofly selected from 1,2-ethylene dichloride, acetonitrile, methylene dichloride, dimethyl sulfoxide (DMSO), chloroform, DMF or tetrahydrofuran (THF).
4. according to a kind of preparation method who has the rhodamine base pH value fluorescent probe of linear response in slightly acidic scope described in claim 2 or 3, it is characterized in that in described step (2), acid binding agent is pyridine or triethylamine.
5. according to a kind of preparation method who has the rhodamine base pH value fluorescent probe of linear response in slightly acidic scope described in claim 2 or 3, it is characterized in that in described step (2), column chromatography filler used is aluminum oxide, eluent is that volume ratio is methylene dichloride and the ethanol of 20:1.
6. the rhodamine base pH value fluorescent probe that has linear response in slightly acidic scope claimed in claim 1, is characterized in that described pH value fluorescent probe solution, along with the color that reduces of pH value becomes deeply rose-coloredly from colourless, can be used for open hole detection.
7. the rhodamine base pH value fluorescent probe that has linear response in slightly acidic scope claimed in claim 1, is characterized in that described pH value fluorescent probe energy selectivity identification hydrogen ion, and is not subject to the interference of other Common Cations.
8. the rhodamine base pH value fluorescent probe that has linear response in slightly acidic scope claimed in claim 1, the fluorescence response that it is characterized in that described pH value fluorescent probe has good linearity in pH=5.0-7.0 interval, this probe sensitivity is good, fluorescence quantum yield when pH=5.13 reaches 0.599, and this probe can detect for the pH value of biomass cells.
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| CN105348293A (en) * | 2015-09-25 | 2016-02-24 | 海南医学院 | Preparation and application of Al<3+> fluorescent probe based on rhodamine B derivative |
| CN109342382A (en) * | 2018-11-23 | 2019-02-15 | 复旦大学 | A kind of preparation method of the depickling functional paper with pH response fluorescence probe |
| CN110862819A (en) * | 2019-11-14 | 2020-03-06 | 南通大学 | PH fluorescent probe based on near-infrared fluorescent dye and preparation method and application thereof |
| CN112500420A (en) * | 2020-11-26 | 2021-03-16 | 江苏大学 | Double-color fluorescent probe and preparation method and application thereof |
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| CN112500420A (en) * | 2020-11-26 | 2021-03-16 | 江苏大学 | Double-color fluorescent probe and preparation method and application thereof |
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| CN103992791B (en) | 2016-08-24 |
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