CN102206235A - Phosphorescent iridium complex capable of dissolving in water system, and preparation method thereof - Google Patents
Phosphorescent iridium complex capable of dissolving in water system, and preparation method thereof Download PDFInfo
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- CN102206235A CN102206235A CN2011100688770A CN201110068877A CN102206235A CN 102206235 A CN102206235 A CN 102206235A CN 2011100688770 A CN2011100688770 A CN 2011100688770A CN 201110068877 A CN201110068877 A CN 201110068877A CN 102206235 A CN102206235 A CN 102206235A
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Abstract
The invention relates to a phosphorescent iridium complex capable of dissolving in a water system, and a preparation method thereof, and specifically relates to a preparation method for water-soluble cysteine and high-cysteine phosphorescent probes based on an iridium complex, and application thereof in the fields of cell marking and imaging, belonging to the technical field of chemical/biological sensors. By the complex material, an aldehyde group in a C^N complex and an amino group and a sulfydryl group in cysteine and high-cysteine generate cyclization reaction to produce a thiazole ring, thus enhancing the phosphorescent emission of the iridium complex; and water solubility is realized by an N^N complex containing a quaternary ammonium salt, a phosphate, a sulfonate and a carboxylate, thus realizing the detection of cysteine and high-cysteine in an aqueous solution.
Description
Technical field
The invention belongs to the chemical/biological sensors technical field, be specifically related to preparation method and the application in cell marking, imaging field thereof of a class based on the water-soluble semi Gelucystine and the homocysteine phosphorescence probe of complex of iridium.
Background technology
Containing the amino acid of sulfydryl such as halfcystine and homocysteine (Fig. 1) plays a part crucial to keeping the Human Physiology balance.For example, the growth of halfcystine and homocysteine pair cell and organism inner tissue organ is absolutely necessary.The shortage of halfcystine can cause serious HUMAN HEALTH problem, as poor growth, hair decolouring, skin injury, muscle and fat loss and liver damage etc.And it is dangerous more to lack homocysteine, and it can cause diseases such as senile dementia, cardiovascular disorder and osteoporosis.So it is significant to detect halfcystine and homocysteine.
The molecular structure of halfcystine and homocysteine
In the technology of existing detection of biological mercaptan, fluorescence chemical sensor is used widely with versatility because of it is easy.Compare organic fluorescence, have d
6, d
8And d
10The phosphorescence heavy metal complex of electronic structure has excellent photophysical property, can be easy to differentiation as big Stokes shift excites and emission peak, can use visible light to excite, long emission lifetime helps the duration of service resolution techniques and separate with the signal to noise ratio that improves detection and sensitivity etc. with the background fluorescence signaling zone effectively.
Yet most metal complexes phosphorescence probe only limits to detect halfcystine and the homocysteine in the organic solution.Up to the present, only the minority probe can detect halfcystine and homocysteine in the cell by fluorescence confocal microscope.Its key issue is the water-soluble bad of the present metal complexes phosphorescence probe of being reported, realize detecting in the cell halfcystine and homocysteine, water and organic solvent be that imaging experiment is essential as the mixed solvent of dimethyl sulfoxide (DMSO), and the organic solvent pair cell have toxicity.Therefore, be necessary to develop brand-new, complete water-soluble metal complexes halfcystine and homocysteine phosphorescence probe and viable cell phosphorescence probe.
Summary of the invention
Technical problem: the object of the present invention is to provide the phosphorescent iridium complex of a class water soluble system, provide their preparation method, and propose this class title complex in detection halfcystine and homocysteine and the application in cell marking, imaging thereof.Utilize uv-visible absorption spectra, fluorescence emission spectrum to detect the response performance of title complex to halfcystine and homocysteine.
Technical scheme: the phosphorescent iridium complex of water soluble system of the present invention has following structural formula:
Wherein,
BF
4 -, Cl
-Or Br
-, R represents respectively:
Wherein,
Br
-Or I
-, Z=H or Na.Preparation method's route is as follows:
Specifically be with 4-(2-pyridyl)-phenyl aldehyde and IrCl
33H
2O is 3 in the ratio of mixture of cellosolvo and water: back flow reaction is 24 hours in the solvent of 1/v: v, dichloro bridge intermediate that obtains and o-phenanthroline derivative, ratio of mixture at methylene dichloride and methyl alcohol is 2: refluxed 4 hours in the solvent of 1/v: v, adding needs the ion salt stirring at room of exchange after 1 hour then, screw out solvent, the solid that gets is separated with column chromatography method, promptly obtain described complex of iridium.
Beneficial effect: the structure that characterizes complex of iridium material and intermediate by nucleus magnetic resonance (NMR), chromaticness online (GCMS), ground substance assistant laser parsing time-of-fight mass spectrometry (MALDI-TOF-MS) etc., utilize adding that ultra-violet absorption spectrum, fluorescence emission spectrum detect halfcystine and homocysteine to photophysical property, and to the influence of energy transfer process.
The amino of aldehyde radical and halfcystine and homocysteine and sulfydryl generation cyclization generate thiazole ring in the C^N part of the present invention, cause the phosphorescent emissions of complex of iridium to strengthen; Utilization contains quaternary ammonium salt, phosphoric acid salt, and sulfonate, the N^N part of carboxylate salt is realized water-soluble, thereby is implemented in the aqueous systems detection to halfcystine and homocysteine.
Description of drawings
Fig. 1. the synthetic title complex is to the ultraviolet-visible spectrum variation diagram of halfcystine and homocysteine among the present invention.Fig. 1 a is a halfcystine, and Fig. 1 b is a homocysteine.
Fig. 2. the synthetic title complex is to the fluorescence emission spectrum variation diagram of halfcystine and homocysteine among the present invention.Fig. 2 a is a halfcystine, and Fig. 2 b is a homocysteine.
Fig. 3. the selectivity test of synthetic title complex among the present invention.
Embodiment
The present invention proposes to be used for detecting in aqueous systems the phosphorescent iridium complex of halfcystine and homocysteine, and its concrete structure formula is:
Wherein,
BF
4 -, Cl
-Or Br
-, R can represent respectively:
Wherein,
Br
-Or I
-, Z=H or Na.
Its system synthetic route of the water-soluble phosphorescence complex of iridium that the present invention proposes is as follows:
Specifically be with 4-(2-pyridyl)-phenyl aldehyde and IrCl
33H
2(3: 1/v: back flow reaction is 24 hours v) at the mixed solvent of cellosolvo and water for O, dichloro bridge intermediate that obtains and o-phenanthroline derivative are at the mixed solvent (2: 1/v: refluxed 4 hours v) of methylene dichloride and methyl alcohol, adding needs the ion salt stirring at room of exchange after 1 hour then, screw out solvent, the solid that gets is separated with column chromatography method, promptly obtain described complex of iridium.
Have being applied as of water-soluble phosphorescence complex of iridium: the detection of halfcystine and homocysteine, cell marking and imaging.
In order to understand the content of patent of the present invention better, further specify technical scheme of the present invention below by concrete example.Specifically comprise synthetic, property testing, titration experiments.But these embodiment do not limit the present invention.
The preparation of embodiment 1, water-soluble complex of iridium:
Compound 1:5-nitro-1, the preparation of 10-o-phenanthroline
Add 5g 1 in round-bottomed flask, 10-o-phenanthroline hydrate adds the 30mL concentrated sulfuric acid dissolution, dropwise adds the 15mL nitrosonitric acid then, and heated solution makes its temperature remain on 160-170 ℃, and reaction refluxed 2 hours.Reaction finishes, and makes it be cooled to room temperature, afterwards solution is poured in the frozen water.Add concentration and be 10% sodium hydroxide solution pH is adjusted to 3.The yellow mercury oxide of separating out is a product, and suction filtration is washed and dry in a vacuum with clear water.Get 5g (88%) faint yellow solid.GC-MS(EI-m/z)：225(M
+)
Compound 2:5-amino-1, the preparation of 10-o-phenanthroline
With 1.889g 5-nitro-1, the 10-o-phenanthroline is dissolved in the 150mL dehydrated alcohol, adds 0.378g 5%Pd/C catalyzer, is heated to 70 ℃ under nitrogen protection, dropwise adds 150mL dehydrated alcohol and 1.3g hydrazine hydrate mixed solution then, back flow reaction 5h.After reaction is finished, allow it be cooled to room temperature, filtered while hot is fallen the Pd/C catalyzer, with washing with alcohol for several times.Filtrate is boiled off most of ethanol, and yellow solid is separated out in cooling, suction filtration, and drying is used ethyl alcohol recrystallization, gets yellow needle-like solid (1.42g, 76%).
1HNMR(400MHz，CDCl
3)9.21(d，1H)，8.95(d，1H)，8.28(d，1H)，7.99(d，1H)，7.66(dd，1H)，7.52(dd，1H)，6.9(s，1H)，4.3(s，2H).
The preparation of compound 3:N^N part (cpa)
With 0.3g 5-amino-1, the 10-o-phenanthroline is dissolved in the 55mL anhydrous tetrahydro furan, adds the 0.22mL triethylamine, stirs 30min under nitrogen protection.Mixed solution is reduced to 0 ℃ then, dropwise add the mixed solution of 5mL tetrahydrofuran (THF) and 0.22mL chloroacetyl chloride, stirred overnight at room temperature.After reaction is finished, clean with 5% sodium bicarbonate aqueous solution, collected organic layer is spin-dried for, and water and ether clean, and gets brown solid (0.241g; 59%).
1HNMR(400MHz，CDCl
3)9.26(d，1H)，9.18(d，1H)，8.95(s，1H)，8.38(s，1H)，8.33(d，1H)，8.26(d，1H)，7.72-7.75(dd，1H)，7.66-7.69(dd，1H)，4.43(s，2H).
The preparation of compound 4:4-(2-pyridyl)-phenyl aldehyde dichloro bridge
Take by weighing IrCl
33H
2O (1mmol) and 4-(2-pyridyl)-phenyl aldehyde (2.5mmol) joins in the there-necked flask, vacuumizes on biexhaust pipe-inflated with nitrogen-vacuumize, and circulates three times, uses the nitrogen protection reaction system at last.(3: 1/v: v) be injected in the reaction system with syringe, stir, and reaction system is warming up to 110 ℃, the reaction times is about 24 hours, has precipitation to generate in the reaction process with the mixture of cellosolvo and water.Reaction system is cooled to room temperature, and then with sedimentation and filtration, and water, ethanol wash, and obtains solid product, promptly.Productive rate: 68%
Compound 5: complex of iridium [Ir (bpa)
2Cpa]
+PF
6 -Preparation
Take by weighing iridium dichloro endo compound 121mg and N^N part (cpa) 68mg joins in the two-neck bottle, add 15mL CH again
2Cl
2Mixed solvent (2: 1/v: v), reflux under magnetic stirs with methyl alcohol.After 4 hours, reduce to room temperature, add 5 times of normal Potassium Hexafluorophosphate (KPF
6), continuing stir about after 1 hour, vacuum rotary steam removes and desolvates, and the gained solid mixture is dissolved in again the CH of about 10mL
2Cl
2In, insolubles is removed by filter, filtrate decompression is revolved steaming, and the gained solid separates the pure product that obtain with column chromatography (methylene dichloride/acetone) except that desolvating afterwards.Productive rate: 69%
1H NMR (400MHz, CDCl
3) 9.76 (d, 2H), 9.24 (s, 1H), 8.80 (d, 1H), 8.52-8.55 (d, 2H), 8.23 (d, 1H), 8.19 (d, 1H), 8.04-8.09 (dd, 2H), 7.84-7.91 (m, 4H), 7.74-7.77 (dd, 1H), and 7.58-7.61 (t, 2H), 7.43-7.46 (t, 2H), 7.11-7.13 (t, 1H), 7.11-7.13 (t, 1H), 7.05-7.07 (t, 1H), 6.80-6.83 (d, 2H), 4.40 (d, 2H).
Compound 6: complex of iridium [Ir (bpa)
2Pto] PF
6 -Preparation at N
2Under the protective condition, 1 normal complex of iridium is dissolved in the dimethyl formamide solution, drips 10 equivalent triethylamines, be warming up to 110 ℃ of backflow stirring reactions 3 hours; After being cooled to room temperature, screw out dimethyl formamide solution, will revolve solid separate with column chromatography method after being dissolved in a small amount of methylene dichloride, revolve except that developping agent and vacuum-drying, promptly obtain water-soluble complex of iridium.Productive rate: 37%
1H NMR (400MHz, CDCl
3) 9.76 (s, 2H), 8.75 (s, 1H), 8.55 (d, 1H), 8.19 (d, 1H), 8.06-8.09 (t, 3H), 7.84-7.91 (m, 5H), 7.68-7.72 (dd, 1H), 7.58-7.60 (m, 2H), 7.42 (d, 1H), 7.38 (d, 1H), 7.03-7.07 (t, 2H), 7.02-7.10 (m, 2H), 6.81-6.84 (dd, 2H), and 3.66-3.72 (dd, 6H), 1.46-1.49 (t, 9H) .m/e 893.7 (M-PF
6).
Embodiment 2: title complex is tested the ultraviolet-visible spectrum of halfcystine and homocysteine response: the complex solution (pure water is made solvent) that disposes 20 μ M, pipette the 2mL complex solution in the fluorescence cuvette, be added dropwise to the 0-200eq pure water gradually and make the halfcystine and the homocysteine solution of solvent, until reaching balance (being no longer considerable change of spectrum), record respectively and do not add and drip the halfcystine of different content and the luminous spectrogram of ultraviolet-visible of homocysteine, as Fig. 1.Test data shows: along with the adding of halfcystine and homocysteine, near the absorption peak 320nm and the 430nm descends.
Embodiment 3: title complex is tested the fluorescence emission spectrum of halfcystine and homocysteine response: the complex solution (pure water is made solvent) that disposes 20 μ M, pipette the 2mL complex solution in the fluorescence cuvette, be added dropwise to the 0-200eq pure water gradually and make the halfcystine and the homocysteine solution of solvent, until reaching balance (being no longer considerable change of spectrum), record respectively and do not add and drip the halfcystine of different content and the fluorescence emission spectrogram of homocysteine, as Fig. 2.Test data shows: along with the adding of halfcystine and homocysteine, emissive porwer increases gradually.
Embodiment 4: selectivity experiment: dispose the complex solution (pure water is made solvent) of 20 μ M, pipette the 2mL complex solution in the fluorescence cuvette, add the different aminoacids that the 200eq pure water is made solvent respectively, test after reaching balance, as Fig. 3.Test data shows: such title complex does not have response to other amino acid except that halfcystine and homocysteine.
Embodiment 5: the viable cell imaging experiment:
Complex of iridium is mixed with the solution of 10mmol, pipettes 20uL solution and make its concentration dilution to 10 μ M in the buffered soln to 2000uL PBS.Get 2mL solution incubated cell and use PBS buffer solution for cleaning cell 3-5 time after 30 minutes, with 405nm wavelength activated cell co-focusing imaging, Z scanning.Test data shows: water-soluble complex of iridium has the good cell penetrance, is distributed in the tenuigenin zone.
Claims (2)
1. the phosphorescent iridium complex of a water soluble system is characterized in that this complex of iridium has following structural formula:
Wherein,
BF
4 -, Cl
-Or Br
-, R represents respectively:
Wherein,
Br
-Or I
-, Z=H or Na.
2. the preparation method of the phosphorescent iridium complex of a water soluble system as claimed in claim 1 is characterized in that preparation method's route is as follows:
Specifically be with 4-(2-pyridyl)-phenyl aldehyde and IrCl
33H
2O is 3 in the ratio of mixture of cellosolvo and water: back flow reaction is 24 hours in the solvent of 1/v: v, dichloro bridge intermediate that obtains and o-phenanthroline derivative, ratio of mixture at methylene dichloride and methyl alcohol is 2: refluxed 4 hours in the solvent of 1/v: v, adding needs the ion salt stirring at room of exchange after 1 hour then, screw out solvent, the solid that gets is separated with column chromatography method, promptly obtain described complex of iridium.
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Cited By (10)
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|---|---|---|---|---|
| CN102928392A (en) * | 2012-10-29 | 2013-02-13 | 山西大学 | Cysteine detection method |
| CN103183677A (en) * | 2013-05-03 | 2013-07-03 | 南京信息工程大学 | Application of ammonium thiosulfate as reducing agent in preparation of 5-amino-1,10-phenanthroline |
| CN104086596A (en) * | 2014-05-08 | 2014-10-08 | 南京邮电大学 | Phosphorescent iridium complex, and preparation method and application thereof |
| CN104098606A (en) * | 2014-05-08 | 2014-10-15 | 南京邮电大学 | Phosphorescent ionic iridium complex and preparation method and application thereof |
| CN105223171A (en) * | 2015-08-31 | 2016-01-06 | 赣南师范学院 | A kind of synthesis of near infrared phosphorescent iridium complex and fluoroscopic examination imaging applications thereof |
| CN108535233A (en) * | 2018-05-17 | 2018-09-14 | 南京邮电大学 | One kind is for hypochlorous water-soluble phosphorescence nano-particle of ratio method detection and the preparation method and application thereof |
| CN108997439A (en) * | 2018-09-11 | 2018-12-14 | 福州大学 | A kind of metal iridium complex and its application based on the preparation of 5- aldehyde radical -1,10- phenanthroline |
| CN108997409A (en) * | 2018-08-28 | 2018-12-14 | 山东省宁津县浩润科技有限公司 | A method of reducing ethyl alcohol in polysulfide silanes coupling agent |
| CN109053814A (en) * | 2018-09-19 | 2018-12-21 | 湖南文理学院 | A kind of fluorescence probe ruthenium complex, synthetic method and its application |
| CN115368870A (en) * | 2022-10-06 | 2022-11-22 | 北京师范大学 | Supermolecule adhesive with long afterglow luminescence property and preparation method thereof |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102928392A (en) * | 2012-10-29 | 2013-02-13 | 山西大学 | Cysteine detection method |
| CN103183677A (en) * | 2013-05-03 | 2013-07-03 | 南京信息工程大学 | Application of ammonium thiosulfate as reducing agent in preparation of 5-amino-1,10-phenanthroline |
| CN103183677B (en) * | 2013-05-03 | 2015-07-01 | 南京信息工程大学 | Application of ammonium thiosulfate as reducing agent in preparation of 5-amino-1,10-phenanthroline |
| CN104086596B (en) * | 2014-05-08 | 2017-01-25 | 南京邮电大学 | Phosphorescent iridium complex, and preparation method and application thereof |
| CN104086596A (en) * | 2014-05-08 | 2014-10-08 | 南京邮电大学 | Phosphorescent iridium complex, and preparation method and application thereof |
| CN104098606A (en) * | 2014-05-08 | 2014-10-15 | 南京邮电大学 | Phosphorescent ionic iridium complex and preparation method and application thereof |
| CN104098606B (en) * | 2014-05-08 | 2016-11-23 | 南京邮电大学 | A kind of Phosphorescent ionic type iridium complex and its preparation method and application |
| CN105223171B (en) * | 2015-08-31 | 2018-03-27 | 赣南师范大学 | A kind of synthesis of near-infrared phosphorescent iridium complex and its fluoroscopic examination imaging applications |
| CN105223171A (en) * | 2015-08-31 | 2016-01-06 | 赣南师范学院 | A kind of synthesis of near infrared phosphorescent iridium complex and fluoroscopic examination imaging applications thereof |
| CN108535233A (en) * | 2018-05-17 | 2018-09-14 | 南京邮电大学 | One kind is for hypochlorous water-soluble phosphorescence nano-particle of ratio method detection and the preparation method and application thereof |
| CN108535233B (en) * | 2018-05-17 | 2020-07-17 | 南京邮电大学 | Water-soluble phosphorescent nanoparticles for detecting hypochlorous acid by ratio method and preparation method and application thereof |
| CN108997409A (en) * | 2018-08-28 | 2018-12-14 | 山东省宁津县浩润科技有限公司 | A method of reducing ethyl alcohol in polysulfide silanes coupling agent |
| CN108997439A (en) * | 2018-09-11 | 2018-12-14 | 福州大学 | A kind of metal iridium complex and its application based on the preparation of 5- aldehyde radical -1,10- phenanthroline |
| CN108997439B (en) * | 2018-09-11 | 2020-09-01 | 福州大学 | Metal iridium complex prepared based on 5-aldehyde-1, 10-phenanthroline and application thereof |
| CN109053814A (en) * | 2018-09-19 | 2018-12-21 | 湖南文理学院 | A kind of fluorescence probe ruthenium complex, synthetic method and its application |
| CN109053814B (en) * | 2018-09-19 | 2020-10-27 | 湖南文理学院 | Fluorescent probe ruthenium complex, and synthesis method and application thereof |
| CN115368870A (en) * | 2022-10-06 | 2022-11-22 | 北京师范大学 | Supermolecule adhesive with long afterglow luminescence property and preparation method thereof |
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Application publication date: 20111005 |