CN110272429A - The light-operated role in fluorescent molecule switch of acid resistance and its synthetic method in a kind of organic solution - Google Patents
The light-operated role in fluorescent molecule switch of acid resistance and its synthetic method in a kind of organic solution Download PDFInfo
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Abstract
The present invention provides the light-operated role in fluorescent molecule switch of acid resistance and its synthetic method in a kind of organic solution, the specific molecular structure of the molecular switch replaces rhodamine spiramide dyestuff as basic structural unit using 3- primary amine or secondary amine, and structural formula is such as shown in (1).The present invention, which develops the light-operated role in fluorescent molecule switch of acid resistance in organic solution, has acidproof performance, and remains photoactivation performance.Therefore the dyestuff of this kind of acid resistance photoactivation can be applied to the sensing detection in organic solvent, avoid the interference of fluorescence background caused by acidic environment.In addition, the light-operated role in fluorescent molecule switch of acid resistance is also used as fluorescence probe applied to sensing and detection field in organic solution in the present invention.
Description
Technical field
The invention belongs to molecular switch fields, and in particular in a kind of organic solution the light-operated role in fluorescent molecule switch of acid resistance and
Its synthetic method.
Background technique
Rhodamine is one kind using xanthene as the dyestuff of parent, the interconversion molecular structure with loop coil and open loop.Rhodamine
Have many advantages, such as that good light stability, molar extinction coefficient are big, fluorescence quantum yield is high compared to other fluorescent dyes, thus by
Extensive concern.Fluorescence " bright-dark " state of rhodamine is switched based on amide loop coil, and rhodamine is in addition to good
Optical property outside, it is also a very big advantage that structure, which is easy to modify, usually carries out simple structure to rhodamine parent
Modifying or introduce some recognition groups can be used to detect.Before probe is in conjunction with target molecule, in the rhodamine of closed loop configuration
Amide is almost without fluorescence, when recognition group is made under the synergistic effect of carbonyl with certain heavy metal species or transition metal ions
Used time can lead to the lactam bond fracture of probe, form open loop structure, fluorescence intensity be caused to significantly increase, to realize to this
The Selective recognition of ion.Highly selective, highly sensitive due to having the characteristics that, rhodamine fluorescence probe is in heavy metal and mistake
It crosses in the detection of metal ion and is widely applied.
Although the characteristics of rhodamine is widely used, environment sensitive also limits it in some extreme environments
Detectability.Other than metal ion can make spiramide open loop, in acid condition, hydrionic attack can equally lead to sieve
Ring-opening reaction occurs for red bright amide loop coil, to generate strong fluorescence.And in actually detected industrial wastewater, outside removing heavy metals ion
Often containing in a large amount of acidic materials, such as the etching waste liquor that generates in printed circuit board production process nearly 60% is acid chlorization
Copper waste etching solution.If being used to detect the heavy metal ion in these acid waste liquids for traditional rhodamine spiramide dyestuff, acid
The fluorescence that activation generates can severe jamming fluorescence signal authenticity, it is entirely ineffective to result even in dyestuff photoactivation performance, because
This this fluorochrome has significant limitation when for the detection of acidic environment intermediate ion.In conclusion acid proof Luo Dan
Bright spiramide class fluorescent switch dyestuff seems especially urgent and important for the exploitation in extreme environment, such as strong acidic environment.
Summary of the invention
It is described organic the present invention provides the light-operated role in fluorescent molecule switch of acid resistance and its synthetic method in a kind of organic solution
The light-operated role in fluorescent molecule switch of acid resistance in solution replaces rhodamine spiramide dyestuff as structural unit, grinds using 3- primary amine or secondary amine
Study carefully this kind of switch dyestuff of discovery has acidproof characteristic in organic phase, that is, shows as the spiramide part in acidic environment and meet matter
Open loop isomerization reaction does not occur when sub- attack, keeps unstressed configuration state.After this kind of resistance to acid dye is dissolved in organic solvent, it is being added
Change in fluorescence is not generated after strong acid, its open loop can only be made to generate fluorescence signal by illumination, enables it when being applied to detection
Substantially reduce the background fluorescence interference in acidic environment, thus this kind of dyestuff have in environment measuring and Material Field it is potential huge
Big application prospect.
The structural formula of the light-operated role in fluorescent molecule switch of acid resistance is as follows in a kind of organic solution of the present invention:
Wherein: R1For H, CH3、CO CH3、SO2CH3Or SO2C6H5CH3
R2For n-Bu, C6H5。
The light-operated role in fluorescent molecule switch of acid resistance in a kind of organic solution, shown in structural formula is one of following,
Synthetic route is as follows:
Specific step is as follows for the synthesis:
(1) 3- nitro rhodamine and n-butylamine are dissolved in dehydrated alcohol by the mass ratio of the material 1:1-20, are warming up to reflux,
Evaporating solvent under reduced pressure after stirring 1-4 hours, intermediate rhodamine 3- nitro butyramide pass through silica gel column chromatography separating-purifying；
(2) product rhodamine 3- nitro butyramide in above-mentioned steps (1) is taken to be dissolved in volume ratio all for 1-5:1 methanol and two
Chloromethanes mixed solvent stirs 1-3 hours under atmosphere of hydrogen and the palladium carbon catalysis for accounting for reactant quality percentage 0.5-10%,
Filtrate is filtered and taken, rhodamine 3- amino-butanamide product is obtained after evaporating solvent under reduced pressure；
(3) product rhodamine 3- amino-butanamide and acyl chlorides in above-mentioned steps (2) is taken to dissolve by the mass ratio of the material 1:1-30
The evaporating solvent under reduced pressure after anhydrous methylene chloride, stirring at normal temperature 1-3 hours, the butyramide for finally replacing rhodamine 3- amide produce
Object is purified by pillar layer separation.
(4) take in above-mentioned steps (2) product rhodamine 3- amino-butanamide, iodomethane and potassium carbonate three by the amount of substance
It is dissolved in anhydrous acetonitrile than 1:1-20:5-30, evaporating solvent under reduced pressure after being added stirring at normal temperature 1-3 hours, finally by rhodamine
The butyramide product that 3- monomethylamine replaces is purified by pillar layer separation.
The light-operated role in fluorescent molecule switch of acid resistance in a kind of organic solution, structural formula is as follows,
Synthetic route is as follows:
(1) it is dissolved in 1,2- dichloroethanes by the mass ratio of the material 1:3-20 by 3- nitro rhodamine and with phosphorus oxychloride, risen
For temperature to flowing back, solvent is evaporated off after 1-3 hours in stirring, and thick acid chloride intermediate is dissolved in anhydrous methylene chloride, is then added dropwise three
Ethamine and aniline mixed solution, wherein the mass ratio of the material of thick acid chloride intermediate, triethylamine and aniline three is 1:0.5-2:1-
2, evaporating solvent under reduced pressure after 8-24 hours is stirred at room temperature, intermediate rhodamine 3- nitro benzamide is purified through chromatographic column；
(2) product rhodamine 3- nitro benzamide in above-mentioned steps (1) is taken to be dissolved in volume ratio all for 1-5:1 methanol and two
Chloromethanes mixed solvent stirs 1-3 hours under atmosphere of hydrogen and the palladium carbon catalysis for accounting for reactant quality percentage 0.5-10%,
Filtrate is filtered and taken, rhodamine 3-AB product is obtained after evaporating solvent under reduced pressure；
The application of the light-operated role in fluorescent molecule switch of acid resistance in organic solution, based on its acid resistance advantage and as fluorescent switch
Application is in numerous areas such as the sensings and detection of biology and chemical substance.
Rhodamine spiramide is a kind of common dyestuff, and closed loop configuration does not have fluorescence, and some metal ions can lead to
Crossing chemical action makes dyestuff that open loop occur, and issues strong fluorescence, and the variation of " bright-dark " signal is usually used in environment measuring neck
Domain.However in some more harsh environments, such as acid organic liquid waste, hydrionic attack also results in spiramide and opens
Ring generates fluorescence, and acid active process, which occurs, will affect the authenticity of fluorescence signal, even results in dyestuff and loses photoactivation performance, because
Application of this this kind of dyestuff in acidic environment is greatly limited.
The 3- primary amine or secondary amine that the present invention develops replace rhodamine spiramide to have acidproof performance, and remain light and swash
Active energy (as shown in Figure 2).Therefore the dyestuff of this kind of acid resistance photoactivation can be applied to the sensing detection in organic solvent, keep away
Exempt from the interference of fluorescence background caused by acidic environment.In addition, acid proof 3- primary amine or secondary amine replace rhodamine spiral shell in the present invention
Amides dyestuff is also used as fluorescence probe and is applied to sensing and detection field.
Detailed description of the invention
Fig. 1: for the P1-P4 of embodiment 1-4 preparation, in methylene chloride/methanol (9/1, v/v) in the mixed solvent, (concentration is
10-5M the time resolution ultraviolet-visible absorption spectroscopy and visible photo) being separately added into before and after trifluoroacetic acid (2.3 μ L, 1000eq) become
Change.
Fig. 2 are as follows: the loop coil and fluorescence for the rhodamine spiramide molecule that the acid resistance 3- primary amine or secondary amine of photoinduction replace are opened
The schematic diagram of pass.
Specific embodiment
The present invention gives the synthetic method of the compound of the light-operated role in fluorescent molecule switch of acid resistance in a kind of organic solution and
Spectrum.
Embodiment 1
Molecule (P1) synthetic route and product structure are as follows:
Synthesis step and characterization: 3- nitro rhodamine (5mmol, 2.4g) and n-butylamine (20mmol, 1.4g) are dissolved in nothing
Water-ethanol (50mL).78 DEG C of reflux, evaporating solvent under reduced pressure after stirring 8 hours are warming up to, product is separated by silica gel chromatographic column
It purifies (petrol ether/ethyl acetate, 8:1v/v), obtained buff powder (2.6g, 95%).Then the powder is all dissolved in
Ethanol/methylene (50mL, 3:1v/v) in the mixed solvent is catalyzed by palladium carbon (0.21g, 10%wt) under an atmosphere of hydrogen
Reduction, suction filtration take filtrate, final white powdered product (2g, 98%) are obtained after evaporating solvent under reduced pressure.
Product has carried out nuclear-magnetism and mass spectrographic characterization:1H NMR(400MHz,CDCl3) δ 7.14 (t, J=7.6Hz, 1H),
6.56 (t, J=8.2Hz, 3H), 6.41-6.25 (m, 5H), 3.34 (dd, J=13.4,6.5Hz, 8H), 3.05 (s, 2H),
1.24-1.04 (m, 16H), 0.68 (t, J=7.1Hz, 3H).13C NMR(101MHz,CDCl3)δ169.59,154.86,
153.08,148.63,144.95,133.24,129.03,114.15,113.31,112.11,108.04,106.77,97.69,,
64.59,44.33,39.70,30.64,20.32,13.57,12.57ppm.LC-MS (ESI): m/z: calculated value: 512.3151,
Experiment value: 513.3220 [M+H]+。
Through above-mentioned detection, identify that its structure is shown in P1.
Product P1 is dissolved in methylene chloride/methanol (9/1, v/v) in the mixed solvent (concentration 10-5M), into mixed solution
It is separately added into trifluoroacetic acid (2.3 μ L, 1000eq).It tests the ultraviolet-visible absorption spectroscopy that acid adding surrounding time is differentiated and shooting can
Photo under light-exposed, as shown in Figure 1, P1 the characteristic absorption peak of rhodamine open loop structure does not occur with acidificatoin time after acid adding
The phenomenon that extending and enhancing, solution colour still maintain colourless, it was demonstrated that P1 has acid resistance.
Embodiment 2
Molecule (P2) synthetic route and product structure are as follows:
Synthesis step and characterization: by P1 (0.25g, 0.5mmol), iodomethane (0.28g, 2mmol) and potassium carbonate (0.34g,
It 2.5mmol) is mixed in acetonitrile (8mL), return stirring 10 hours, is obtained by filtration filtrate after being cooled to room temperature, evaporating solvent under reduced pressure,
Crude product by column chromatography (silica gel, petrol ether/ethyl acetate, 10:1v/v) separating-purifying obtain white powder P2 (0.17g,
65%).
Product has carried out nuclear-magnetism and mass spectrographic characterization:1H NMR(400MHz,CDCl3) δ 7.23 (t, J=7.9Hz, 1H),
6.75 (d, J=4.9Hz, 1H), 6.57 (t, J=9.3Hz, 2H), 6.49 (d, J=8.1Hz, 1H), 6.41-6.22 (m, 5H),
3.33 (q, J=7.0Hz, 8H), 3.04 (s, 2H), 2.97 (d, J=4.9Hz, 3H), 1.16 (t, J=6.9Hz, 12H), 1.07
(s, 4H), 0.67 (t, J=6.5Hz, 3H).13C NMR(101MHz,CDCl3)δ170.15,154.93,153.09,148.60,
147.23,133.78,129.01,113.08,110.19,108.01,107.53,106.74,97.67,44.33,39.63,
30.69,29.42,20.30,13.60,12.57.LC-MS (ESI): m/z: calculated value: 526.3308；Experiment value: 527.3523
[M+H]+。
Through above-mentioned detection, identify that its structure is shown in P2.
Product P2 is dissolved in methylene chloride/methanol (9/1, v/v) in the mixed solvent (concentration 10-5M), into mixed solution
It is separately added into trifluoroacetic acid (2.3 μ L, 1000eq).It tests the ultraviolet-visible absorption spectroscopy that acid adding surrounding time is differentiated and shooting can
Photo under light-exposed, as shown in Figure 1, P2 the characteristic absorption peak of rhodamine open loop structure does not occur with acidificatoin time after acid adding
The phenomenon that extending and enhancing, solution colour still maintain colourless, it was demonstrated that P2 has acid resistance.
Embodiment 3
Molecule (P3) synthetic route and product structure are as follows:
Synthesis step and characterization: P1 (0.25g, 0.5mmol) and chloroacetic chloride (58mg, 0.75mmol) are mixed in dichloromethane
Alkane (5mL), evaporating solvent under reduced pressure after stirring 2 hours, crude product pass through column chromatography (silica gel, petrol ether/ethyl acetate, 8:1v/v)
Separating-purifying obtains white powder P3 (0.26g, 95%).
Product has carried out nuclear-magnetism and mass spectrographic characterization:1H NMR(400MHz,CDCl3) δ 10.60 (s, 1H), 8.43 (d, J=
8.2Hz, 1H), 7.39 (t, J=7.9Hz, 1H), 6.74 (d, J=7.6Hz, 1H), 6.46 (d, J=8.8Hz, 2H), 6.38 (d,
J=2.6Hz, 2H), 6.28 (dd, J=8.9,2.6Hz, 2H), 3.34 (q, J=7.0Hz, 8H), 3.06 (t, J=7.0Hz,
2H), 2.29 (s, 3H), 1.17 (t, J=7.0Hz, 12H), 1.12-1.02 (m, 4H), 0.69 (t, J=6.7Hz, 3H).13C
NMR(101MHz,CDCl3)δ169.30,168.85,158.27,153.50,153.27,148.83,136.75,133.81,
128.78,117.95,117.52,116.43,108.07,105.32,101.26,99.97,97.72,65.17,44.36,
39.98,30.41,24.97,20.35,13.55,12.55.LC-MS (ESI): m/z: calculated value: 554.3257；Experiment value:
555.3382[M+H]+。
Through above-mentioned detection, identify that its structure is shown in P3.
Product P3 is dissolved in methylene chloride/methanol (9/1, v/v) in the mixed solvent (concentration 10-5M), into mixed solution
It is separately added into trifluoroacetic acid (2.3 μ L, 1000eq).It tests the ultraviolet-visible absorption spectroscopy that acid adding surrounding time is differentiated and shooting can
Photo under light-exposed, as shown in Figure 1, P3 the characteristic absorption peak of rhodamine open loop structure does not occur with acidificatoin time after acid adding
The phenomenon that extending and enhancing, it was demonstrated that P3 has acid resistance.
Embodiment 4
Molecule (P4) synthetic route and product structure are as follows:
Synthesis step and characterization: P1 (0.25g, 0.5mmol) and paratoluensulfonyl chloride (95mg, 0.5mmol) are mixed in
Methylene chloride (5mL), stirring 3 hours after evaporating solvent under reduced pressure, crude product by column chromatography (silica gel, petrol ether/ethyl acetate,
6:1v/v) isolated yellow powder P4 (0.30g, 91%).
Product has carried out nuclear-magnetism and mass spectrographic characterization:1H NMR(400MHz,CDCl3) δ 9.88 (s, 1H), 7.83 (d, J=
8.3Hz, 2H), 7.51 (d, J=8.1Hz, 1H), 7.32-7.25 (m, 3H), 6.67 (d, J=7.5Hz, 1H), 6.35 (d, J=
1.9Hz, 2H), 6.28-6.14 (m, 4H), 3.33 (q, J=7.1Hz, 8H), 2.99 (t, J=7.0Hz, 2H), 2.41 (s, 3H),
1.16 (t, J=7.0Hz, 12H), 1.07-0.96 (m, 4H), 0.67 (t, J=6.8Hz, 3H).13C NMR(101MHz,CDCl3)
δ167.92,153.86,153.14,148.78,143.49,136.52,135.47,133.45,129.43,128.58,
127.52,118.59,118.03,117.21,107.90,105.02,97.67,65.03,44.34,39.76,30.25,
21.55,20.19,13.54,12.50.LC-MS (ESI): m/z: calculated value: 666.3240；Experiment value: 667.3211 [M+H]+。
Through above-mentioned detection, identify that its structure is shown in P4.
Product P4 is dissolved in methylene chloride/methanol (9/1, v/v) in the mixed solvent (concentration 10-5M), into mixed solution
It is separately added into trifluoroacetic acid (2.3 μ L, 1000eq).It tests the ultraviolet-visible absorption spectroscopy that acid adding surrounding time is differentiated and shooting can
Photo under light-exposed, as shown in Figure 1, P4 the characteristic absorption peak of rhodamine open loop structure does not occur with acidificatoin time after acid adding
The phenomenon that extending and enhancing, solution colour still maintain colourless, it was demonstrated that P4 has acid resistance.
Embodiment 5
Molecule (P5) synthetic route and product structure are as follows:
Synthesis step and characterization: 3- nitro rhodamine (2mmol, 1.12g) and aniline (2mmol, 0.186g) are dissolved in nothing
Water-ethanol (5mL).78 DEG C of reflux, evaporating solvent under reduced pressure after stirring 4 hours are warming up to, product passes through column chromatography (silica gel, petroleum
Ether/ethyl acetate, 6:1v/v) isolated light yellow solid (1.08g, 96%).Then the solid product is all dissolved in
Methanol and methylene chloride (5mL, 3:1v/v) in the mixed solvent stir 1 hour under atmosphere of hydrogen and palladium carbon (10%wt) catalysis,
Filtrate is filtered and taken, final white solid product (1.01g, 99%) is obtained after evaporating solvent under reduced pressure.
Product has carried out nuclear-magnetism and mass spectrographic characterization:1H NMR(400MHz,CDCl3) δ 7.22 (t, J=7.7Hz, 1H),
7.14-7.04 (m, 3H), 6.85-7.74 (m, 4H), 6.60 (d, J=7.9Hz, 1H), 6.40 (d, J=7.4Hz, 1H), 6.33
(dd, J=8.8,2.5Hz, 2H), 6.24 (d, J=2.5Hz, 2H), 5.41 (s, 2H), 3.31 (q, J=7.1Hz, 8H), 1.14
(t, J=7.0Hz, 12H).13C NMR(101MHz,CDCl3)δ169.30,154.56,152.84,148.60,145.57,
136.55,133.97,128.86,128.40,127.15,126.32,113.40,113.33,112.15,108.03,107.08,
97.67,67.10,44.25,12.55.LC-MS (ESI): m/z: calculated value: 532.2838, experiment value: 533.2840 [M+H]+。
Through above-mentioned detection, identify that its structure is shown in P5.
Product P5 is dissolved in methylene chloride/methanol (9/1, v/v) in the mixed solvent (concentration 10-5M), into mixed solution
It is separately added into trifluoroacetic acid (2.3 μ L, 1000eq).It tests the ultraviolet-visible absorption spectroscopy that acid adding surrounding time is differentiated and shooting can
Photo under light-exposed, there is not the characteristic absorption peak of rhodamine open loop structure in P5 after acid adding as the result is shown, and solution colour is still
Keep colourless, it was demonstrated that P5 has acid resistance.
Claims (7)
1. the light-operated role in fluorescent molecule switch of acid resistance in a kind of organic solution, it is characterised in that: its structural formula is as follows,
Wherein: R1For H, CH3、CO CH3、SO2CH3Or SO2C6H5CH3
R2For n-Bu, C6H5。
2. the light-operated role in fluorescent molecule switch of acid resistance in organic solution according to claim 1, it is characterised in that: its structural formula
Shown in one of following,
3. the synthetic method of the light-operated role in fluorescent molecule switch of acid resistance, feature exist in organic solution according to claim 2
In: specific step is as follows for the synthesis:
(1) 3- nitro rhodamine and n-butylamine are dissolved in dehydrated alcohol by the mass ratio of the material 1:1-20, are warming up to reflux, stirred
Evaporating solvent under reduced pressure after 1-4 hours, intermediate rhodamine 3- nitro butyramide pass through silica gel column chromatography separating-purifying；
(2) product rhodamine 3- nitro butyramide in above-mentioned steps (1) is taken to be dissolved in volume ratio all for 1-5:1 methanol and dichloromethane
Alkane mixed solvent is stirred 1-3 hours under atmosphere of hydrogen and the palladium carbon catalysis for accounting for reactant quality percentage 0.5-10%, is filtered
And filtrate is taken, rhodamine 3- amino-butanamide product is obtained after evaporating solvent under reduced pressure；
(3) product rhodamine 3- amino-butanamide and acyl chlorides is taken in above-mentioned steps (2) to be dissolved in nothing by the mass ratio of the material 1:1-30
Water methylene chloride, evaporating solvent under reduced pressure after stirring at normal temperature 1-3 hours finally lead to the butyramide product that rhodamine 3- amide replaces
Cross pillar layer separation purification.
(4) take in above-mentioned steps (2) product rhodamine 3- amino-butanamide, iodomethane and potassium carbonate three by the mass ratio of the material 1:
1-20:5-30 is dissolved in anhydrous acetonitrile, evaporating solvent under reduced pressure after being added stirring at normal temperature 1-3 hours, finally that rhodamine 3- is mono-
The butyramide product that methylamine replaces is purified by pillar layer separation.
4. the synthetic method of the light-operated role in fluorescent molecule switch of acid resistance, feature exist in organic solution according to claim 3
In: the acyl chlorides is chloroacetic chloride, paratoluensulfonyl chloride or mesyl chloride.
5. the light-operated role in fluorescent molecule switch of acid resistance in organic solution according to claim 1, it is characterised in that: its structural formula
Are as follows:
6. the synthetic method of the light-operated role in fluorescent molecule switch of acid resistance, feature exist in organic solution according to claim 5
In: specific step is as follows for the synthesis:
(1) 3- nitro rhodamine and aniline are dissolved in dehydrated alcohol by the mass ratio of the material 1:1-20, are warming up to reflux, stir 1-
Evaporating solvent under reduced pressure after 4 hours, intermediate rhodamine 3- nitro butyramide or rhodamine 3- nitro benzamide pass through silicagel column color
Compose separating-purifying；
(2) product rhodamine 3- nitro benzamide in above-mentioned steps (1) is taken to be dissolved in volume ratio all for 1-5:1 methanol and dichloromethane
Alkane mixed solvent is stirred 1-3 hours under atmosphere of hydrogen and the palladium carbon catalysis for accounting for reactant quality percentage 0.5-10%, is filtered
And filtrate is taken, rhodamine 3-AB product is obtained after evaporating solvent under reduced pressure.
7. in a kind of organic solution according to claim 1 the light-operated role in fluorescent molecule switch of acid resistance super-resolution fluorescence at
Picture, molecular probe, fluorescence sense and detection and the application of other field.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0141962A1 (en) * | 1983-09-15 | 1985-05-22 | The Hilton - Davis Chemical Company | Hydrazine derivatives of fluorans and use thereof in electrochromic recording systems |
| US20130150254A1 (en) * | 2010-12-09 | 2013-06-13 | John J. Naleway | Reagents and methods for direct labeling of nucleotides |
| CN105153214A (en) * | 2015-10-30 | 2015-12-16 | 中国人民解放军第二军医大学 | Silicon-based rhodamine-nitrogen oxide fluorescent probe and preparation method and application thereof |
| CN105646511A (en) * | 2016-03-19 | 2016-06-08 | 云南中烟工业有限责任公司 | Rhodamine 6G-based mercury ion detection fluorescent probe molecule, preparation method and application |
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2018
- 2018-03-16 CN CN201810217650.XA patent/CN110272429B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0141962A1 (en) * | 1983-09-15 | 1985-05-22 | The Hilton - Davis Chemical Company | Hydrazine derivatives of fluorans and use thereof in electrochromic recording systems |
| US20130150254A1 (en) * | 2010-12-09 | 2013-06-13 | John J. Naleway | Reagents and methods for direct labeling of nucleotides |
| CN105153214A (en) * | 2015-10-30 | 2015-12-16 | 中国人民解放军第二军医大学 | Silicon-based rhodamine-nitrogen oxide fluorescent probe and preparation method and application thereof |
| CN105646511A (en) * | 2016-03-19 | 2016-06-08 | 云南中烟工业有限责任公司 | Rhodamine 6G-based mercury ion detection fluorescent probe molecule, preparation method and application |
Non-Patent Citations (1)
| Title |
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| QINGKAI QI ET AL.: ""A H-bond strategy to develop acid-resistant photoswitchable rhodamine spirolactams for super-resolution single-molecule localization microscopy"", 《CHEMICAL SCIENCE》 * |
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