CN103614135B - Two-photon fluorescent probe as well as preparation method and application thereof - Google Patents
Two-photon fluorescent probe as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a two-photon fluorescent probe as well as a preparation method and an application thereof. The structure of the two-photon fluorescent probe is shown in the specification. The two-photon fluorescent probe presents relatively high selectivity and high sensitivity in a coexisting system of aminothiopropionic acid or homocysteine and other amino acids. The cytotoxicity test shows that the two-photon fluorescent probe almost has no toxicity on cells. The two-photon fluorescent microscopic imaging experiment shows that the two-photon fluorescent probe is good in permeability on 293FT cells. The two-photon fluorescent probe is suitable for detecting the distribution of amino acid micromolecules in the cells.
Description
One, technical field
The present invention relates to a kind of two-photon fluorescence probe, Its Preparation Method And Use, can by halfcystine or homocysteine in two-photon imaging qualitative detection cell.
Two, background technology
Amino acid such as halfcystine, homocysteine and gsh play an important role in biosystem.They have identical structural formula, when these amino acid whose concentration acquire a certain degree, can cause a series of disease, and such as growth slowdown, hair bleaching, oedema, drowsiness, liver injury, muscle and fat reduce, dermatosis and Alzheimer's disease.How detecting them is very important and the interest causing a lot of scientist.But in cell, detect amino acid molecular qualitatively still seldom, therefore detect amino acid small molecules in vivo and in vitro particularly important.
Fluorescent probe is in certain system, and when physical property a certain in a kind of material or system changes, the molecule of corresponding change can occur fluorescent signal.The advantages such as fluorescence spectrum is easy to detect due to it, sensitive present superior performance in trace detection.
Quinoline has good spectral response curve and water-soluble, and is also hypotoxicity to cell.Therefore quinoline is a good fluorescent reporter group.The document that quinoline has been reported as fluorophore is a lot, but major part is confined to single photon fluorescence probe, and two-photon fluorescence probe report is very few.The two-photon fluorescence probe that fluorescent probe detects halfcystine/homocysteine is more rare.
It is single photon fluorescence probe that current halfcystine/homocysteine detects fluorescent probe major part, but single photon fluorescence probe not only easily makes Bio-ontology produce autofluorescence interference, and short excitation wavelength also can produce photic poison to cell.In recent years, two-photon fluorescence probe is as an interested research topic of scientist, start progressively to replace single photon fluorescence probe, two-photon fluorescence probe have that near infrared excites, dark-field imaging, avoid fluorescent bleach and photic poison, determine target activation, the advantage such as high lateral resolution, reduction biological tissue uptake factor and the interference of reduction tissue autofluorescence.
Three, summary of the invention
The present invention aims to provide a kind of two-photon fluorescence probe and its production and use, technical problem to be solved selects suitable fluorescent probe structure by molecular designing, to realize halfcystine or homocysteine in two-photon imaging qualitative detection cell, have the advantage that selectivity is single-minded, highly sensitive, detectable level is low, cytotoxicity test shows that the present invention does not almost have toxic action to cell.
Two-photon fluorescence probe of the present invention take quinoline as parent, and be called for short fluorescent probe or fluorescent probe molecule (NQ), its structure is expressed from the next:
The preparation method of two-photon fluorescence probe of the present invention, operates according to the following steps:
(1) the hydrochloric acid 100mL of paraiodoaniline 15g (68.49mmol) and 6mol/L is added in reactor, be warming up to 105 DEG C, treat that solid dissolves in backward reactor completely and drip crotonic aldehyde 12g (171mmol), insulation reaction to track to raw material reaction with TLC complete, room temperature is cooled to after reaction terminates, reaction solution is poured in 200mL water, be extracted with ethyl acetate to remove unreacted crotonic aldehyde, aqueous phase ammonia neutralization to pH value is 8, be extracted with ethyl acetate again, merge organic phase, organic phase anhydrous sodium sulfate drying also obtains crude product after revolving steaming, intermediate 1 is obtained after recrystallization (solvent is ethyl acetate and the sherwood oil mixed solvent that forms of 1:20 by volume),
(2) intermediate 18g (29.74mmol) is added in round-bottomed flask, add 1,4-dioxane dissolves, be heated to 60 DEG C subsequently, a tin anhydride 0.82g (7.43mmol) is added every ten minutes, the total amount that adds of tin anhydride is 4.95g, be warming up to 80 DEG C of reactions 2.5 hours, room temperature is cooled to after reaction terminates, filter and use Isosorbide-5-Nitrae-dioxane washing, collecting organic phase, obtain crude product after revolving steaming, crude product uses column chromatography purification (methylene dichloride is as eluent) and obtains intermediate 2;
(3) by intermediate 24g (14.13mmol), 4-(N, N-dimethyl) phenylacetylene 2.08g (14.13mmol), triphenyl phosphorus palladium chloride 0.1g (0.14mmol), cuprous iodide 0.5g(2.6mmol) and triethylamine 10mL add in round-bottomed flask, add toluene to dissolve, room temperature reaction 8 hours, filtering and collecting filter liquid, obtain crude product after filtrate being revolved steaming, after recrystallization (solvent is ethyl acetate and the sherwood oil mixed solvent that forms of 1:5 by volume), obtain two-photon fluorescence probe NQ.
The building-up process of fluorescent probe molecule NQ of the present invention is as follows:
The application of two-photon fluorescence probe of the present invention as detection reagent when halfcystine or homocysteine in qualitative detection cell.
Fluorescent probe molecule of the present invention is dissolved in the mother liquor of obtained 1mM in DMSO, gets this mother liquor of 250 μ L in 10mL volumetric flask, then use DMSO constant volume, be mixed with 25 μMs.Same method gets the mother liquor of 250 μ L in 10mL volumetric flask, then adds halfcystine (Cys) or the homocysteine (Hcy) of 5 times of equivalents.The excitation wavelength of fluorescent probe single photon and two-photon is respectively 395nm and 800nm, and detect the fluorescence spectrum change within the scope of 485-700nm, along with the change of time, 550nm emission peak strengthens (Fig. 3) gradually.
The mechanism that fluorescent probe of the present invention detects halfcystine or homocysteine is that on fluorescent probe molecule, aldehyde radical and halfcystine or homocysteine react the thiazolidine forming ring-type, there is strong ICT process in fluorescent probe molecule itself, therefore by the impact of solvent, fluorescent probe molecule itself shows very weak fluorescence.After adding halfcystine or homocysteine, ICT process disappears, and solvent effect obviously weakens, and strengthens gradually along with the emission peak at about 550nm.Such purpose of design is to realize the detection of halfcystine or homocysteine.
Fluorescent probe molecule fluorescence quantum yield of the present invention is lower, and after reacting with halfcystine or homocysteine, fluorescence quantum yield raises about 10 times.Therefore fluorescent probe molecule of the present invention can better applying biological detect in.
Fluorescent probe molecule of the present invention can carry out narrow spectrum identification to the halfcystine of biomass cells system or homocysteine, monitoring analysis and tracking.
Fluorescent probe molecule structure of the present invention is simple, is easy to synthesis, and action site and fluorophor are an entirety.Fluorescent probe molecule of the present invention and halfcystine or homocysteine have clear and definite action site, and the present invention forms the thiazolidine stablizing ring-type after being reacted by aldehyde radical and halfcystine or homocysteine.Fluorescent probe molecule of the present invention detects halfcystine or homocysteine with the change of fluorescence power, and can find out the change (solution colour becomes colourless from yellow) of front and back solution colour under visible light.After fluorescent probe molecule of the present invention and halfcystine or homocysteine effect, under ultraviolet lamp, naked eyes just can find out its change in fluorescence, and fluorescence color is from without becoming yellow-green light, simple to operate, rapid sensitive.Fluorescent probe molecule selectivity of the present invention is single-minded, highly sensitive, and detectable level is low (is less than 10
-7m).
Four, accompanying drawing explanation
Fig. 1 is fluorescent probe molecule of the present invention and halfcystine or homocysteine reaction process figure.
Fluorescent probe molecule of the present invention (25 μMs) is added the ultraviolet of Cys and Hcy of 5 times of equivalents along with time variations spectrogram by Fig. 2.From Fig. 3 a, 3b(illustration) in can find out that, after Cys and Hcy adding 5 times of equivalents, about after half hour, fluorescence intensity tends towards stability.
Fluorescent probe molecule of the present invention (25 μMs) is added Cys and Hcy(0-80 μM by Fig. 3) fluorescence intensity spectrogram, the solution of every bar line is all test after standing 30 minutes.As can be seen from Figure 3, after Cys and Hcy adding 3 times of equivalents, fluorescence intensity tends towards stability.
Fig. 4 is fluorescent probe molecule NQ(1mM of the present invention) add 5 times of equivalent halfcystines or homocysteine excites the change of lower Shuangzi absorption cross section value at different wavelength.
Fig. 5 is that fluorescent probe molecule of the present invention is at the cell survival rate of cell cultures after 24 hours.As can be seen from Fig. 4 we, when concentration is 10 μMs, cell survival rate also has about 98%, describes fluorescent probe molecule of the present invention to cytotoxic effect, therefore can be used for doing cell detection and follow the tracks of halfcystine/homocysteine.
Fig. 6 is the two-photon fluorescence co-focusing imaging photo of fluorescent probe molecule of the present invention, wherein scheme the light field that A is 293FT cell, figure B is that fluorescent probe molecule (10 μMs) is in cell cultures after 30 minutes, rinse with PBS damping fluid (pH7.4), at two-photon fluorescence confocal microscopic image, under 800nm excites, fluorescent emission capture range 500-600nm.Figure C is under figure B same treatment, then adds Cys(50 μM), continue culturing cell and cultivate 30 minutes, rinse with PBS damping fluid (pH7.4), at two-photon fluorescence confocal microscopic image, under 800nm excites, phosphor collection scope 500-600nm.As can be seen from cell imaging, fluorescent probe molecule NQ fluorescence in cell is very weak, and after Cys process, fluorescence obviously strengthens.
Five, embodiment
Below by embodiment, the present invention will be further described.
Embodiment 1: the synthesis of fluorescent probe molecule NQ
1, the synthesis of intermediate 1
Take the hydrochloric acid 100mL of paraiodoaniline 15g (68.49mmol) and 6mol/L in there-necked flask, device prolong, be heated to 105 DEG C, until solid dissolves completely, slowly drip crotonic aldehyde 12g (171mmol), raw material reaction is tracked to complete with TLC, stopped reaction, be cooled to room temperature, reaction solution is poured in 200mL water, be extracted with ethyl acetate (100mL × 2) to remove the complete crotonic aldehyde of unreacted, aqueous solution ammonia neutralization to pH value is 8, extraction into ethyl acetate (50mL × 2), merge organic phase, organic phase anhydrous sodium sulfate drying, be spin-dried for obtain crude product, crude product recrystallization in the mixed solvent of ethyl acetate and sherwood oil (volume ratio 1:20) obtains 14.45g (53.72mmol) intermediate 1, yield 78.4%.
1H NMR(400MHz,CDCl
3,ppm):δ2.74(3H,d,J=17.5Hz),7.28(1H,t,J=7.3Hz),7.76-7.69(1H,m),7.92-7.86(2H,m),8.13(1H,s).
13C NMR(100MHz,CDCl
3,ppm):δ25.44,76.75,77.07,77.39,90.87,122.69,128.23,130.39,134.93,136.20,138.08,146.77,159.70.
2, the synthesis of intermediate 2
Take intermediate 18g (29.74mmol) in round-bottomed flask, add 1, 4-dioxane dissolves completely to solid, be heated to 60 DEG C, a tin anhydride 0.82g (7.43mmol) is added every ten minutes, about within 1 hour, add complete (total amount 4.95g), be warming up to 80 DEG C and continue reaction 2.5 hours, after reaction terminates, be cooled to room temperature, suction filtration disgorging, with 1, 4-dioxane rinses (5mL × 2), collect and merge organic phase, organic phase is revolved and is steamed to obtain crude product, crude product column chromatography purification (eluent is methylene dichloride) obtains the intermediate 2 of 7.56g (6.61mmol), yield 89.9%.
1H NMR(400MHz,CDCl
3,ppm)δ7.96(1H,d,J=8.9Hz),8.05(2H,t,J=9.1Hz),8.20(1H,d,J=8.5Hz),8.32(1H,s),10.20(1H,s).
13C NMR(100MHz,CDCl
3,ppm):δ76.72,77.04,77.35,95.77,118.14,131.39,131.84,136.15,136.72,139.40,146.82,152.86,193.35.
3, the synthesis of fluorescent probe molecule NQ
Under nitrogen protection; take intermediate 24g (14.13mmol); 4-(N; N-dimethyl) phenylacetylene 2.08g (14.13mmol); triphenyl phosphorus palladium chloride 0.1g (0.14mmol); cuprous iodide 0.5g(2.6mmol) and triethylamine 10mL in round-bottomed flask; add toluene to dissolve; room temperature reaction 8 hours; filtering and collecting filter liquid; obtain crude product after filtrate being revolved steaming, crude product recrystallization in the mixed solvent of ethyl acetate and sherwood oil (volume ratio 1:5) obtains 3.5g (12.68mmol) target product, yield 89.74%.
1H NMR(400MHz,CDCl
3,ppm):δ3.03(6H,s),6.69(2H,d,J=8.4Hz),7.47(2H,d,J=8.5Hz),7.88(1H,d,J=8.7Hz),8.03(2H,d,J=8.6Hz),8.17(1H,d,J=8.8Hz),8.25(1H,d,J=8.3Hz),10.19(1H,d,J=14.5Hz).
13C NMR(100MHz,CDCl
3,ppm):δ40.26,88.64,94.45,100.70,109.48,111.87,118.03,122.98,125.58,129.93,133.13,136.83,152.46,193.66.
Embodiment 2: the two-photon test of fluorescent probe molecule
Utilize two-photon measuring technology, test the two photon absorption cross section that fluorescent probe molecule (NQ) and fluorescent probe molecule and halfcystine react rear (MQ-Cys), as can be seen from Figure 4, after fluorescent probe molecule and halfcystine or homocysteine react, the maximum absorption cross section of (NQ-Cys or NQ-Hcy) is 587 and 693GM respectively, and two-photon excitation wavelength is all at 800nm.Embodiment 3: cytotoxicity is tested
MTT(3-(4,5-dimethylthiazole-2)-2,5-diphenyltetrazolium bromide bromine salt) experiment is according to the article reported, does the test of some cytotoxicities.In with a collection of cell, add 0 respectively, 10,30, the fluorescent probe molecule of 80 μMs, this condition be 37 DEG C, containing 5%CO
2cell culture incubator in hatch 24 hours, the formula according to cell survival degree: cell survival rate %=OD570(sample)/OD570(control group) × 100, can be regarded as to obtain cell survival rate (Fig. 5).As can be seen from Fig. 5 we, when concentration is 10 μMs, cell survival rate also has about 98%, describes fluorescent probe molecule of the present invention to cytotoxic effect, therefore can be used for doing cell detection and follow the tracks of amino acid small molecules.
Embodiment 4: cell imaging is tested
293FT cell is by DEME(invitrogen) nutrient solution cultivates, imaging the day before yesterday, 293FT cell is put in flat bottom surface ware, during imaging the fluorescent probe MQ of 293FT cell and 10 μMs DMSO solution in 37 DEG C, containing 5%CO
2cell culture incubator in hatch 0.5 hour, after fully washing with the PBS buffered soln of neutrality or nutrient solution, use two-photon fluorescence co-focusing imaging, obtain Fig. 6 b.In the above-mentioned cell culture fluid containing fluorescent probe, add (50 μMs) cysteine solution, 37 DEG C, containing 5%CO
2cell culture incubator in hatch 0.5 hour, after fully washing with the PBS buffered soln of neutrality or nutrient solution, then carry out two-photon fluorescence co-focusing imaging, obtain Fig. 6 c.As can be seen from Figure 5, before adding halfcystine, 500-60nm has faint fluorescence; After adding halfcystine, 500-600nm fluorescence obviously strengthens.
Claims (3)
1. a two-photon fluorescence probe, is be parent with quinoline, it is characterized in that its structure is expressed from the next:
2. a preparation method for two-photon fluorescence probe according to claim 1, is characterized in that operating according to the following steps:
(1) the hydrochloric acid 100mL of paraiodoaniline 15g and 6mol/L is added in reactor, be warming up to 105 DEG C, dissolve completely in backward reactor and drip crotonic aldehyde 12g, insulation reaction is complete to raw material reaction, room temperature is cooled to after reaction terminates, reaction solution is poured into water, be extracted with ethyl acetate to remove unreacted crotonic aldehyde, aqueous phase ammonia neutralization to pH value is 8, be extracted with ethyl acetate again, merge organic phase, organic phase anhydrous sodium sulfate drying also obtains crude product after revolving steaming, obtains intermediate 1 after recrystallization;
(2) 8g intermediate 1 is added in round-bottomed flask, add Isosorbide-5-Nitrae-dioxane to dissolve, be heated to 60 DEG C subsequently, add tin anhydride 4.95g, be warming up to 80 DEG C of reactions 2.5 hours, be cooled to room temperature after reaction terminates, filter and use 1,4-dioxane washs, collect organic phase, obtain crude product after revolving steaming, crude product uses column chromatography purification and obtains intermediate 2; The middle tin anhydride of step (2) is divided into six times and adds, and the interval time at every turn added is 10 minutes;
(3) by 4g intermediate 2,4-(N, N-dimethyl) phenylacetylene 2.08g, triphenyl phosphorus palladium chloride 0.1g, cuprous iodide 0.5g and triethylamine 10mL add in round-bottomed flask, add toluene to dissolve, room temperature reaction 8 hours, reaction terminates rear filtration, collect filtrate, obtain crude product after filtrate being revolved steaming, after recrystallization, obtain two-photon fluorescence probe NQ.
3. a purposes for two-photon fluorescence probe according to claim 1, is characterized in that: the application as detection reagent when halfcystine or homocysteine in qualitative detection cell.
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| CN104371707A (en) * | 2014-10-31 | 2015-02-25 | 山东师范大学 | Fluorescent probe and preparation method thereof, and application in detecting superoxide anions |
| CN104557601B (en) * | 2015-01-19 | 2017-01-04 | 天水师范学院 | For identifying the monomer of halide anion and polymer and preparation method |
| CN104877672A (en) * | 2015-05-27 | 2015-09-02 | 济南大学 | Two-photon fluorescent probe for identifying palladium (0) and preparation method and application of two-photon fluorescent probe |
| CN104876863B (en) * | 2015-05-29 | 2017-02-22 | 北京农学院 | Fluorescent probe compound and preparation method and application thereof |
| CN104829526B (en) * | 2015-05-29 | 2017-06-09 | 北京农学院 | Fluorescent probe compounds and its preparation method and application |
| CN105801479B (en) * | 2016-04-29 | 2018-02-02 | 安徽大学 | A kind of two-photon viscosity fluorescence probe and its production and use |
| CN105906619B (en) * | 2016-05-18 | 2018-11-06 | 安徽大学 | A kind of two-photon fluorescence probe and its preparation method and application |
| CN106946773B (en) * | 2016-12-27 | 2019-06-18 | 安徽大学 | A kind of Ratio-type two-photon formaldehyde fluorescence probe and its preparation method and application |
| CN108484479B (en) * | 2018-05-18 | 2021-02-26 | 安徽大学 | Carbazolyl two-photon fluorescent probe and preparation method and application thereof |
| CN108727261B (en) * | 2018-06-21 | 2021-09-24 | 济南大学 | Preparation method of nitro-substituted quinaldine |
| CN109456264B (en) * | 2018-11-30 | 2021-03-30 | 华南理工大学 | Fluorescent probe for detecting nitroreductase, preparation method thereof and application of enzymatic reaction |
| CN110156630B (en) * | 2019-05-17 | 2022-02-08 | 曲阜师范大学 | Two-photon ultralow background fluorescent probe and preparation method and application thereof |
| CN112479998B (en) * | 2020-11-16 | 2022-03-15 | 广州中医药大学(广州中医药研究院) | Dihydroquinoline fluorescent probe and preparation method and application thereof |
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| EP2523937B1 (en) * | 2010-01-12 | 2015-03-11 | Centre National De La Recherche Scientifique | Multiphoton activable quinoline derivatives, their preparation and their uses |
| CN102127055B (en) * | 2010-11-25 | 2012-12-12 | 山东大学 | Single-photon and two-photon homocysteine fluorescent probes and use thereof |
| CN103351335A (en) * | 2013-05-28 | 2013-10-16 | 中南大学 | Synthesis of fluorescence enhanced fluorescent molecular probe for detecting mercapto-containing amino acids, and application of probe |
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