CN105062463B - The binuclear ruthenium of different alkyl chain lengths is used as the lysosome probe in cell - Google Patents
The binuclear ruthenium of different alkyl chain lengths is used as the lysosome probe in cell Download PDFInfo
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- CN105062463B CN105062463B CN201510433722.0A CN201510433722A CN105062463B CN 105062463 B CN105062463 B CN 105062463B CN 201510433722 A CN201510433722 A CN 201510433722A CN 105062463 B CN105062463 B CN 105062463B
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Abstract
The application in the association areas such as targeting detection cancer cell lysosome organelle fluorescence probe is used as the invention discloses the binuclear ruthenium of three kinds of different alkyl chain lengths.Complex easily penetration cell film and can be targetted and enter lysosome, for lysosome dyeing；The stoke shift of its luminescence generated by light is larger, it is possible to prevente effectively from cross-color interference；Its photostability is also relatively good, it is adaptable to which prolonged luminescence generated by light monitors the activity of lysosome.
Description
Technical field
This patent belongs to fluorescent biomolecules probe field, is related to binuclear ruthenium and detects cancer cell lysosome in targeting
Application in the association areas such as organelle fluorescence probe.
Background technology
Lysosome is a kind of acidic organelles in eukaryotic, is responsible for digestion, the degradation function of cell, lysosome is thin
(P.Saftig, J.Kl are played an important role in the various vital movements of born of the same parents, including the circulation of metabolism, cell membrane, Apoptosis
μmperman,Nat.Rev.Mol.Cell Biol.2009,10,623–635；G.Kroemer,M.Jaattela,
Nat.Rev.Cancer 2005,5,886–897；M.E.Gμicciardi,M.Leist,G.J.Gores,Oncogene2004,
23,2881–2890).If its generating function is disorderly, the generation of a variety of diseases such as tumour, inflammation, silicosis can be triggered
(Fehrenbacher,N.；Jaattela,M.Cancer Res.2005,65,2993–2995).Lysosome fluorescence probe can
The mark to lysosome is realized, lysosomal location is marked, dynamic change of the lysosome in physiology, pathologic process is intuitively monitored
Change, the molecular mechanism of vital movement is participated in for being fully understood from lysosome, and there is important guidance to the treatment of disease
Meaning.Therefore, study, develop lysosome fluorescence probe there is important theory significance and actual application value.Carry altogether herein
And three binuclear rutheniums can be used as lysosome fluorescence probe, wherein complex Ru2 it has been reported that in document (Liu, P.；
Liu,J.；Zhang,Y.-Q.；Wu,B.-Y.；Wang,K.-Z.J.Photochem.Photobiol.B.2015,143,89-
99), but only discuss its cell absorption property do not study its specific positioning in cell, invention applies cell
Core, mitochondria, three kinds of dyestuffs of lysosome and three complexs are dyed jointly, and three are observed under Laser Scanning Confocal Microscope
The lysosome that the binuclear ruthenium of different alkyl chain lengths is positioned in cell.There is the double-core ruthenium of lysosome stationkeeping ability at present
Coordination compound fluorescent probe has not been reported, and the research provides meaningful for exploitation binuclear ruthenium class lysosome fluorescence probe
Exploration.
The content of the invention
The purpose of the present invention is the binuclear ruthenium for preparing three kinds of different length alkyl chains, apply mtt assay (3- (4,
5- dimethylthiazoles -2) -2,5- diphenyltetrazolium bromide bromides colorimetric method) and high intension analytic approach probed into three complexs to thin
The toxicity of born of the same parents, and common location imaging research has been carried out to three kinds of complexs by fluorescence co-focusing method, with Hoechst 33342
(- 1H- the benzimidazoles of tri-chlorination hydrogen 2- (4- ethylphenyls) -5- (4- methyl isophthalic acids-piperazinyl) -2,5- two), Mitotracker
Tri- kinds of fluorescence probes of green, LysoTracker green are reference material, are analyzed by common location, it was demonstrated that three kinds of complexs are in cancer
The mark to lysosome can be realized in cell.
Technical scheme is as follows：
The part L1 for three kinds of binuclear rutheniums that the present invention is used, L2, L3 represent, three kinds of complexs Ru1, Ru2,
Ru3, is represented, and structure is as follows：
The route of synthesis of above-mentioned binuclear ruthenium is as shown below：
Compared with prior art, the beneficial effects of the present invention are：
The most of probes having now been found that lack special targeting, and can not provide the quantitative letter of object distribution
Breath.In the urgent need to developing with organelle positioning function and can reflect that the fluorescence probe present invention of object distribution is synthesized
Three kinds of complexs can enter in living cells with living cells co-incubation, so specifically enter intracellular lysosome this
Organelle, causes the fluorescence intensity of lysosome to significantly increase, and then for the monitoring of lysosome physiological activity in cancer cell.Together
When ruthenium complex also have that spectrochemical property is stable, extinction coefficient is big, fluorescence lifetime is long compared to traditional lysosome fluorescence probe
With stoke shift it is big the features such as.And the present invention has used the method for high intension analysis to detect the thin of complex medicine for the first time
Cellular toxicity, high intension provide a kind of sensitivity it is high, easy to operate, using safety cell propagation and activity test method, with
Traditional MTT experiment, which is compared, has obvious advantage.
Brief description of the drawings
Cytoactive figure of Fig. 1 HeLa cells after the complex Ru1-Ru3 of various concentrations is incubated 48h
Fig. 2 HeLa cells are after 20 micro- complex Ru1-Ru3 rubbed are incubated 24 hours, with Hoechst 33342 in concentration
The burnt picture of copolymerization after dyeing 30 minutes
Fig. 3 HeLa cells are after 20 micro- complex Ru1-Ru3 rubbed are incubated 24 hours, in Mitotracker in concentration
The burnt picture of copolymerization after being dyed 30 minutes in green and Hoechst 33342
Fig. 4 HeLa cells are after 20 micro- complex Ru1-Ru3 rubbed are incubated 24 hours, in Lysotracker in concentration
The burnt picture of copolymerization after being dyed 30 minutes in green and Hoechst 33342
Embodiment
Embodiment 1：The preparation of ligand L 1, L2, L3 and three ruthenium complexes
1. the preparation of precursor：1,3- bis--(4- aldehyde radicals-carbazyl) propane, 1,6- bis--(4- aldehyde radicals-carbazyl) hexane, 1,
Synthesis reference literature (Zhang Yuqi, Beijing Normal University's master thesis of 10- bis--(4- aldehyde radicals-carbazyl) decane；
Zhang,Y.；Wada,T.and Sasabe,H.Joμrnal of Polymer Science:Part A:Polymer
Chemistry.1996,34,2289-2298；Ostraμskaite,J.；Voska,V.and Grazμleviciμs,
J.V.Monatshefte f ü r Chemie.2002,133,599-607.) in method synthesize.
The synthesis of 2.1,10- Phen -5,6- diketone：The advantage of various kinds of document method is combined, (Amouyal,
E.；Homsi,A.；Chambron,J.-C.and Sauvage,J.-P.J.Chem.Soc.,Dalton Trans.1990,
1841-1845；Hiort,C.；Lincoln,P.and Nordén,B.J.Am.Chem.Soc.1993,115,3448-3454；
Paw,W.and Eisenberg,R.Inorg.Chem.1997,36,2287-2293.；Calderazzo,F.；Marchetti,
F.；Pampaloni, G.and Passarelli, V.J.Chem.Soc., Dalton Trans.1999,4389-4396) experiment
Before should by a hydration Phen (10 grams, 50 mmoles) and KBr (10 grams, 84 mmoles) with mortar it is finely ground after to entering one
In there-necked flask equipped with magneton, seal and refrigerator is put into after mouth freezes a night, in addition, by the concentrated sulfuric acid (100 milliliters) and concentrated nitric acid (50
Milliliter) mix in advance, it is also placed in refrigerator and freezes a night.During experiment, first there-necked flask is put into ice salt bath and freezes a period of time, is loaded onto
Condenser pipe, in the mixed acid slowly frozen along bottle wall addition.When just adding acid, it can be seen that have a small amount of bromine generation, when
After solid is not had by acidleach, the speed for producing bromine slows down.Add after acid, ice bath is removed, allow reaction system to return to room temperature, treat solid
Body completely by acidleach it is saturating after, start to be stirred with magneton, it is seen that have the generation of part bromine.It is slowly heated to 85 DEG C or so reactions 8 small
When, visible during reaction to have substantial amounts of bromine to flow back, solution takes on a red color transparence.After 8 hours, condenser pipe is removed, bottle stopper, oil bath is pulled out
Temperature maintains 85 DEG C or so, removes bromine, about needs the time at night.Stop heating after, while hot by orange solution to enter 1200 milli
Rise in trash ice, solution is in yellow green.Solution is neutralized to pH=5~6 with sodium acid carbonate, if water adds properly, to expected
During pH value, it may appear that substantial amounts of yellow mercury oxide (when water is few, will appear from substantial amounts of salt, cause extraction difficult；When water is more, although heavy
Form sediment and be dissolved, but still can extract product with dichloromethane).Extracted repeatedly with dichloromethane until water layer is in pale pink.
The a small amount of bromine for going to remain in organic layer with a small amount of washing, organic layer anhydrous sodium sulfate drying after filtering, then dichloromethane is steamed
It is dry.Crude product is recrystallized with about 800 milliliters of absolute methanols.When recrystallization solution is diluter pass through Slow cooling, can obtain compared with
Big yellow needle-like crystals, are collected by filtration after product, and filtrate about concentrates half, separate out second part of production again after Slow cooling
Product, filtrate, which continues concentration, can also separate out product.The preceding yield of product that separates out twice is up to more than 50%.Vacuum drying, obtains yellow
Color solid.
3.L1 synthesis：Reference literature synthetic method (Liu, P.；Liu,J.；Zhang,Y.-Q.；Wu,B.-Y.；Wang,
K.-Z.J.Photochem.Photobiol.B.2015,143,89-99), Phendione (0.085g, 0.40 milli
Rub), 1,10- bis--(4- aldehyde radicals-carbazyl) decane (0.11 gram, 0.20 mmoles), ammonium acetate (0.62 gram, 8.10 mmoles) is in 20
In milliliter ethanol, the lower backflow of nitrogen protection 12 hours.Reaction is finished, cooling, is poured into 30 milliliters of water, is stood, and is filtered, washing.
Gained solid DMF/Diethyl ether recrystallization, obtains yellow solid 0.18g, yield 98%.
4.L2 synthesis：Reference literature synthetic method (Liu, P.；Liu,J.；Zhang,Y.-Q.；Wu,B.-Y.；Wang,
K.-Z.J.Photochem.Photobiol.B.2015,143,89-99), weigh 0.2133g (1 mmoles) Phen -5,6-
Diketone, 1.5799g (20 mmoles) ammonium acetate are in 20 milliliters of glacial acetic acid, the lower low-grade fever dissolving of nitrogen protection, and solution is in yellow transparent
Shape, is rapidly added 0.2355g (0.5 mmoles) 1,6- bis--(2,2 ' dialdehyde-baseds-carbazyl) hexane, solution takes on a red color after dissolving
It is bright, agitating and heating 12h at 100 DEG C.React after a few minutes, occur yellow solid reactions in bottle wall and finish, there are a large amount of solids to give birth to
Into being cooled to room temperature, pour into 50 milliliters of water (pH=3), ammonification water (25%) is adjusted to pH=7, now there are a large amount of yellow solids to give birth to
Into, centrifuge, obtained solid is respectively washed three times with water, ethanol, dichloromethane respectively, finally depressurize suction filtration and obtain yellow solid,
Yield 70%.
5.L3 synthesis：Reference literature synthetic method (Liu, P.；Liu,J.；Zhang,Y.-Q.；Wu,B.-Y.；Wang,
K.-Z.J.Photochem.Photobiol.B.2015,143,89-99), by Phendione (0.084 gram, 0.40
Mmoles), 1,3- bis--(4- aldehyde radicals-carbazyl) propane (0.082 gram, 0.19 mmoles), ammonium acetate (0.77 gram, 10.02 mmoles) it is molten
In 20 milliliters of ethanol, the lower backflow of nitrogen protection 13 hours.Reaction is finished, cooling, is poured into 30 milliliters of water, is stood, filtering, water
Wash.With 80 milliliters of DMF dissolving gained solids, filtering.Filtrate concentrates, with DMF/second
Ether is recrystallized.Gained yellow solid is dissolved in as far as possible few DMF, (expansion is separated with thin-layer chromatography
Agent：Methylene chloride/methanol=3/2, volume ratio), with the silica gel obtained by DMF is rinsed, by the N of gained, N-
Dimethyl formamide solution is concentrated, and DMF/Diethyl ether recrystallization is then used again, yellow solid 0.071g is obtained, and is produced
Rate 37%.
6. binuclear ruthenium Ru1 synthesis：L1 (0.081 gram, 0.090 mmoles), two two (2,2- bipyridyls) two of hydration
Ruthenic chloride Ru (bpy)2Cl2·2H2O (0.094 gram, 0.18 mmoles) is stirred in 5 milliliters of ethylene glycol at lower 140 DEG C of nitrogen protection
Reaction 14 hours, reaction solution becomes reddish brown by initial purple, cools down, filtering.Add dropwise when rocking into filtrate
Enter the sodium perchlorate aqueous solution (a perchloric acid hydrate sodium is about 1.4 mmoles), separate out peony precipitation.Stand, suction filtration.Precipitation second
Nitrile/Diethyl ether recrystallization, solid acetonitrile dissolves, and uses column chromatography (solvent：Saturation potassium nitrate solution/water/acetonitrile=1/4/
35, volume ratio), main red zone is collected, revolving removes most of acetonitrile, and adding water dissolves the salt of precipitation, is then added dropwise to
The sodium perchlorate aqueous solution (a perchloric acid hydrate sodium is about 1.4 mmoles), separates out red precipitate.Suction filtration, by gained solid with acetonitrile/
Ether diffusion recrystallization, obtains red solid 0.11g, yield 55%.
7. binuclear ruthenium Ru2 synthesis：Reference literature synthetic method (Liu, P.；Liu,J.；Zhang,Y.-Q.；
Wu,B.-Y.；Wang, K.-Z.J.Photochem.Photobiol.B.2015,143,89-99) synthesis.0.0104 gram of (0.2 milli
Rub) Ru (bpy)2Cl2·2H20th, 0.0852g (0.1 mmoles) ligand Ls 2 and 5 milliliters of ethylene glycol mixing, lower 110 DEG C of N2 gas shieldeds are stirred
Heating 12h is mixed, dropwise addition Isosorbide-5-Nitrae-dioxane in suction filtration, filtrate is then cooled down, grease occurs, pour out supernatant, grease
Dissolved with ethanol, add Isosorbide-5-Nitrae-dioxane and separate out precipitation, the precipitation is recrystallized with ethanol/Isosorbide-5-Nitrae-dioxane, finally
To dark red solid, yield 69%.
8. binuclear ruthenium Ru3 synthesis：L3 (0.073 gram, 0.090 mmoles), Ru (bpy)2Cl2·2H2O(0.094
Gram, 0.18 mmoles) in 5 milliliters of ethylene glycol, stirring reaction 14 hours at lower 140 DEG C of nitrogen protection, reaction solution is by initial
Purple becomes reddish brown, cools down, filtering.The sodium perchlorate aqueous solution (the high chlorine of hydration is added dropwise when rocking into filtrate
Sour sodium is about 2.0 mmoles), separate out peony precipitation.Stand, suction filtration.Precipitation acetonitrile/Diethyl ether recrystallization, solid is molten with acetonitrile
Solution, uses column chromatography (solvent：Saturation potassium nitrate solution/water/acetonitrile=1/4/35, volume ratio), collect main red
Band, revolving removes most of acetonitrile, and adding water dissolves the salt of precipitation, is then added dropwise to the sodium perchlorate aqueous solution (the high chlorine of hydration
Sour sodium is about 2.0 mmoles), separate out red precipitate.Suction filtration, gained solid is recrystallized with acetonitrile/ether diffusion, red solid is obtained
0.10 gram, yield 52%.
Embodiment 2：The cytotoxicity experiment of three ruthenium complexes
Take in the preferable Cervical Cancer HeLa Cells of exponential phase of growth state, be made with culture medium after cell suspension, with cell
Tally is counted, according to 1 × 104Individual cells/well is inoculated in 96 orifice plates, carries out Secondary Culture.After passage 24 hours, by original
Culture medium is suctioned out, and adds the 100 microlitres/hole of culture medium containing various concentrations ruthenium complex (10-80 is micro- to rub), and positive controls add
Enter the 100 microlitres/hole of culture medium containing various concentrations Platinum complexes, negative control group add 100 microlitres of fresh culture/
Hole.96 orifice plates are put into 37 DEG C of relative humidity 95%, 5% CO2gas incubator is incubated 24 hours.Treat complex effect 24
After hour, old culture medium is discarded, lucifuge adds 100 microlitres of culture medium (5 mg/ml MTT containing MTT:Culture medium=1:10)；
It is incubated 4 hours, then adds DMSO lysates 15 minutes；ELIASA densitometric OD490 absorbances.Calculated not according to OD values
With inhibiting rate of the concentration complex to HeLa cells, linear fit is carried out to it by origin, it is 50% institute to read inhibiting rate
Corresponding complex concentration, as IC50 values.Result, tries to achieve complex Ru1, Ru2, Ru3 IC as shown in Figure 150Value is respectively：
13.85,>100,46.72 it is micro- rub/liter, the IC of cis-platinum50Be worth for 6.84 it is micro- rub/liter.Show, complex Ru2 cell toxicant is low, fit
Preferably as cell fluorescence imaging agents.
Embodiment 3：Three complexs are in fluorescence co-focusing positioning experiment intracellular HeLa
Cell is inoculated in 20 square millimeters of confocal microscope culture dish, cell density is 1.0 × 104
Individual/hole, adds fixed concentration ruthenium complex Ru2 (20 micro- rub) culture medium, is put into 37 DEG C of relative humidity 95%, 5% dioxy
Change carbon incubator to be incubated 24 hours, former culture medium is suctioned out, be 10 with concentration with pH=7.4 phosphate rinse solution three times
Micro- lysosome dyestuff LysoGreen for rubbing dyes 2 hours, and 100 receive the mitochondrial dye Mito-Tracker Green dyeing 30 that rubs
Minute, the nucleus dyestuff Hoechst 33342 of 5 mcg/mls is dyed 30 minutes, in configuration Ar/Kr ion emitters
Complex is excited to be imaged with 488 nanometers under ZEISS LSM700 Laser Scanning Confocal Microscopes.Ru2 and Hoechst 33342, (Hoechst
33342 and Mito-Tracker Green), the result of (Hoechst 33342 and LysoGreen) common location be shown in Fig. 2,
In Fig. 3, Fig. 4.As a result show, Ru2 is with LysoGreen common locations in lysosome subcellular organelle.
Claims (1)
1. the lysosome fluoroscopic examination that the binuclear ruthenium of different alkyl chain lengths is used in living cells, the binuclear ruthenium
It is made up of cationic moiety and anionicsite, wherein, cationic moiety is double-core ruthenium cation, and anionicsite is ClO4 -,
Its structure is shown below：
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| CN107118235B (en) * | 2017-05-12 | 2019-05-14 | 北京师范大学 | Application of the near-infrared luminous ruthenium complex in cellular pH sensing |
| CN110967326A (en) * | 2019-12-12 | 2020-04-07 | 北京师范大学 | Near-infrared light-emitting binuclear ruthenium complex as tumor cell recognition and imaging reagent |
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| CN1651444A (en) * | 2004-02-03 | 2005-08-10 | 北京师范大学 | Ruthenium (II) compounding material used for pH sensing and its preparation method |
| CN102344464A (en) * | 2011-07-20 | 2012-02-08 | 北京师范大学 | High water-solubility ruthenium metal complex singlet oxygen fluorescent probe, preparation method thereof, and application thereof |
| CN104464895A (en) * | 2014-09-05 | 2015-03-25 | 北京师范大学 | Binuclear ruthenium complex evaporated film electrode with stable height, preparation method of binuclear ruthenium complex evaporated film electrode and application of binuclear ruthenium complex evaporated film electrode |
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| CN1651444A (en) * | 2004-02-03 | 2005-08-10 | 北京师范大学 | Ruthenium (II) compounding material used for pH sensing and its preparation method |
| CN102344464A (en) * | 2011-07-20 | 2012-02-08 | 北京师范大学 | High water-solubility ruthenium metal complex singlet oxygen fluorescent probe, preparation method thereof, and application thereof |
| CN104464895A (en) * | 2014-09-05 | 2015-03-25 | 北京师范大学 | Binuclear ruthenium complex evaporated film electrode with stable height, preparation method of binuclear ruthenium complex evaporated film electrode and application of binuclear ruthenium complex evaporated film electrode |
Non-Patent Citations (2)
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| 一种含芴基的钌(II)配合物的合成及DNA键合性质;姚威等;《物理化学学报》;20061015;第23卷(第2期);第237-241页 * |
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