CN104086596A - Phosphorescent iridium complex, and preparation method and application thereof - Google Patents
Phosphorescent iridium complex, and preparation method and application thereof Download PDFInfo
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- CN104086596A CN104086596A CN201410194180.1A CN201410194180A CN104086596A CN 104086596 A CN104086596 A CN 104086596A CN 201410194180 A CN201410194180 A CN 201410194180A CN 104086596 A CN104086596 A CN 104086596A
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Abstract
The invention relates to a phosphorescent iridium complex, and a preparation method and an application thereof, belongs to the technical field of organic photoelectric functional materials, and concretely relates to a preparation method of phosphorescent iridium complex molecules, and an application of the phosphorescent iridium complex molecules in molecule oxygen detection, and cell marking and imaging. The above complex material is composed of a cyclomedtalating ligand, a metal center and a benzyl substituted anthracene auxiliary ligand, has a structural general formula shown in the specification, has the advantages of long luminescence life, mild reaction conditions and easy purification, and has very good application prospects in anoxybiotic detection, cell imaging and pathology diagnosis.
Description
Technical field
The invention belongs to organic photoelectrical material technical field, be specifically related to the preparation method of a class phosphorescent iridium complex and the application in molecular oxygen detection, cell marking and imaging field thereof.
Background technology
Oxygen molecule normally plays an important role to organism vital movement, and at inside of human body, the impact of oxygen molecule is mainly divided into two parts, and one is normal bodily tissue, needs oxygen to turn round; Another one, is tumor tissues and bacterium, virus, and they need to just can survive under the environment of detesting.Oxygen participates in all great physiological activity of human body, comprises that Conversion of energy is heat, and eliminate various toxin all to have the participation of oxygen abundance.Oxygen is also used for being oxidized various toxin by health, and bacterium, virus, cancer cells, old cell.Under the state lacking, the normal work of these human bodies all can be subject to great impact, and causes toxin to get rid of, and accumulation is got off, and triggers various fatal diseases.The infringement of for example organ, the most direct reason be this organ at operation process, consumed a large amount of oxygen, produce a large amount of free radicals, and do not obtain oxygen supply timely, in coming and the acidity of health; Diabetics, under anoxic condition, causes sugar to be utilized completely, and causes holding of sugar to stay; Cardiovascular patient, because acidity is destroyed, causes arteriosclerosis, and causes blood circulation to be obstructed, and cause cardiovascular disorder.
Oxygen partial pressure in human body has certain numerical range, when suck, be 20mmHg, inhale when pure oxygen lower than 70mmHg, children are 5mmHg (0.66 kPa), normal young people average out to 8mmHg (1.06 kPas), within 60～80 years old, can reach 24mmHg (3.2 kPas), generally be no more than 30mmHg.The numerical value of oxygen partial pressure shows the appearance of organism illness while departing from normal fluctuation interval, oxygen partial pressure enlarges markedly the oxygenate dysfunction that represents lung.Meanwhile, oxygen partial pressure obviously lowers, and often lower than 60mmHg, generally by due to lung internal short-circuit, as pulmonary atelectasis and adult respiratory distress syndrome, inhales pure oxygen and can not correct.The hypoxemia that moderate increases, generally sucks pure oxygen and is expected to obtain correction, as chronic obstructive disease of lung.Due to the hypoxemia that hypoventilation causes, if PAO2-Pao2 is normal, point out the basic cause of disease mostly not at lung, be probably the alveolar hypoventilation that central nervous system or nerve-muscle changes cause.Therefore, the oxygen molecule in human body exists, and not only participates in the energy supply of life eubolism, and the measurement of oxygen partial pressure deviation value be can be used for to the early diagnosis of illness, makes exploitation have important biological value for detection of the probe of oxygen molecule.
At present, the method that detects oxygen molecule has had a lot of research, the analysis of constant oxygen level is mainly contained to chemical capacity method, magnet and oxide analysing method, zirconium white concentration cell method and vapor-phase chromatography etc., and the analysis of micro-oxygen content mainly contains chemical colorimetry, electrochemical process, coulometry and yellow phosphorus luminescence method etc.Yanqing Tian etc. reported a kind of with polymkeric substance as the novel method of auxiliary matrix, receive and on polymeric film, detect dissolved oxygen by crosslinkable oxygen sensor covalent linkage.The good light stability of this sensor, the time of response of the change to dissolved oxygen is short, and has good biocompatibility, especially to almost no cytotoxicity (Chem.Mater.2010,22,2069 – 2078) of Human Lung gland cancer epithelial cell.Xiangqun Zeng etc. has reported that a kind of ionic liquid is as electrolytical polarography oxygen sensor, and the detectability of this sensor can reach 0.05vol%, and oxygen partial pressure has linear dependence in 0%～20% scope.Compare traditional water design, ionic liquid makes sensor have better detection performance and stability as supporting electrolyte, can be used for the measurement of the oxygen level under non-standard condition, greatly extends (Anal.Chem.2011 the work-ing life of sensor, 83,7066 – 7073).But there is following technical problem in above-mentioned technology fluorescent probe: (1) is although the auxiliary Complex probe of polymkeric substance is reduced its bio-toxicity, but this corsslinking molecular luminous relatively a little less than, phosphorescence intensity before and after weary oxygen changes relatively little, can make the DeGrain of cell imaging.(2) make it in solution, there is good detection performance with ion liquid medium, but be applicable to can have some limitations in biomass cells environment.
Therefore, exploitation has phosphorescence probe efficient, that can be used for biomass cells imaging and has important using value.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of complex of iridium of phosphorescent emissions, provide their preparation method, and propose this application of class title complex in oxygen molecule detection, cell marking and bio-imaging.
The technical solution adopted in the present invention is as follows:
For the technical scheme that solves above-mentioned one of them technical problem proposition is: a kind of complex of iridium of phosphorescent emissions, the complex of iridium being made up of the assistant ligand of cyclic metal complexes, metal center and phenmethyl replacement anthracene has following general structure:
Wherein, C^N part is the one in lower array structure:
The present invention is that the technical scheme that solves above-mentioned another technical problem proposition is: the preparation method's of this phosphorescent iridium complex synthetic route is as follows:
Step 1. under nitrogen protection; in the reaction solution system of ethanol/toluene/salt of wormwood saturated aqueous solution (v:v1:2:1), add methylphenylboronic acid and 9; 10-dibromoanthracene; under the catalysis of four (triphenyl phosphorus) palladium, react 12 hours; reaction stops rear standing cooling; collect organic phase with dichloromethane extraction mixed solution, concentrated obtain crude product and obtain the bromo-10-p-methylphenyl of pure product: 9-anthracene through column chromatography for separation.
Step 2 .1; the two Diphenyl phosphino ferrocene palladium chlorides of 1'-are as catalyzer; 9-bromo-10-p-methylphenyl anthracene and duplex pinacol boric acid ester 80 DEG C of nitrogen protection confined reactions 12 hours in the alkaline environment of dioxane, salt of wormwood; reaction stops first dioxane being steamed and being removed afterwards; then use dichloromethane extraction mixed solution; collect organic phase, concentrate and obtain crude product, obtain pure target product through column chromatography for separation: p-methylphenyl anthracene pinacol boric acid ester.
Step 3. make solvent with m-xylene, 2,5-dibromo pyridine reacts with normal-butyl tin, taking four (triphenyl phosphorus) palladium as catalyzer, 130 DEG C of reactions of lucifuge three days, add disodium EDTA to remove remaining tin reagent after reaction finishes, by dichloromethane extraction mixed solution collection organic phase, concentrated obtain crude product to obtain pure product: 5,5'-bis-through column chromatography for separation bromo-2,2'-dipyridyl.
Step 4. under nitrogen protection; by iridium dichloro bridge and N^N part 40 DEG C of confined reactions 4 hours in methylene chloride/methanol (2:1, v:v) mixed solution, add Potassium Hexafluorophosphate to continue reaction 1 hour after being cooled to room temperature; separating-purifying, obtains complex of iridium intermediate.
Step 5. under nitrogen protection; in the reaction solution system of ethanol/toluene/salt of wormwood saturated aqueous solution (v:v1:2:1), add p-methylphenyl anthracene pinacol boric acid ester and complex of iridium intermediate; under the catalysis of four (triphenyl phosphorus) palladium, react 12 hours; reaction stops rear standing cooling; collect organic phase with dichloromethane extraction mixed solution, concentrated obtain crude product and obtain pure complex of iridium end product through column chromatography for separation.
The present invention is that the technical scheme that solves above-mentioned another technical problem proposition is: this phosphorescent iridium complex is applied to weary oxygen and detects.
The present invention is that the technical scheme that solves above-mentioned another technical problem proposition is: this phosphorescent iridium complex is applied to cell imaging and biomarker.
The invention has the beneficial effects as follows:
(1) assistant ligand that synthetic phosphorescent iridium complex replaces anthracene by cyclic metal complexes, metal center and phenmethyl herein forms, and has relatively long triplet lifetime, can realize the sensitiveer detection to oxygen, has potential using value.
(2) the synthetic phosphorescent iridium complex material of the present invention detects as weary oxygen, and along with the reduction of oxygen concn, phosphorescent emissions significantly strengthens, and is turn-on type phosphorescence probe, and detection effect is remarkable, response is fast.
(3) this probe material has low bio-toxicity, and easily enters in cell cytosol, makes this class probe can be used for weary oxygen in cell and detects, and this is significant to furtheing investigate physiological action and the illness prediction of oxygen molecule in organism body.
Brief description of the drawings:
Fig. 1 is the CH of phosphorescence probe in embodiment 1
3the responsiveness of the phosphorescent emissions spectrum of CN solution to molecular oxygen.
Fig. 2 be in embodiment 1 phosphorescence probe for detection of the Laser Scanning Confocal Microscope photo of molecular oxygen in cell.
Fig. 3 be in embodiment 1 phosphorescence probe for detection of the life-span imaging photo of molecular oxygen in cell.
Fig. 4 is that in embodiment 1, phosphorescence probe adopts the life-span imaging photo of TIME RESOLVED TECHNIQUE for detection of molecular oxygen in cell.
Embodiment
Below in conjunction with Figure of description, the invention is described in further detail.
Embodiment 1
The preparation of the bromo-10-p-methylphenyl of 1.9-anthracene
In round-bottomed flask, add methylphenylboronic acid (2.5mmol) and 9,10-dibromoanthracene (2.0mmol), 80 DEG C of confined reactions 12 hours in the mixed solution of 20mL ethanol/toluene/salt of wormwood saturated aqueous solution (v:v1:2:1), reaction stops rear standing cooling, collect organic phase with dichloromethane extraction mixed solution, concentrated obtain crude product and obtain the bromo-10-p-methylphenyl of pure product: 9-anthracene through column chromatography for separation.Productive rate: 80%.
1H?NMR(400MHz,CDCl
3,298K):δ(ppm)＝2.54(s,3H),7.29(d,J＝8.0Hz,2H),7.35-7.42(m,4H),7.56-7.61(m,2H),7.67-7.71(d,J＝8.8Hz,2H),8.61(d,J＝8.8Hz,2H)。
2. the preparation of p-methylphenyl anthracene pinacol boric acid ester
1, under the catalysis of the two Diphenyl phosphino ferrocene palladium chlorides of 1'-, the bromo-10-p-methylphenyl of 9-anthracene (3.0mmol) and duplex pinacol boric acid ester (3.5mmol) 80 DEG C of confined reactions 12 hours in the alkaline environment of 6mL dioxane, salt of wormwood, reaction stops first dioxane being steamed and being removed afterwards, then use dichloromethane extraction mixed solution, collection organic phase is concentrated obtains crude product, obtains pure target product through column chromatography for separation.Productive rate: 90%.
1H?NMR(400MHz,CDCl
3,298K):δ(ppm)＝1.60(s,12H),2.52(s,3H),7.27-7.33(m,4H),7.36-7.39(d,J＝7.6Hz,2H),7.43-7.48(m,2H),7.64-7.68(d,J＝8.8Hz,2H)。
3.5,5'-bis-is bromo-2, the preparation of 2'-dipyridyl
Make solvent with m-xylene, add 2,5-dibromo pyridine (5.0mmol) reacts with normal-butyl tin (5.5mmol), taking four (triphenyl phosphorus) palladium as catalyzer, 130 DEG C of reactions of lucifuge three days, reaction adds disodium EDTA to remove remaining tin reagent after finishing, and collects organic phase with dichloromethane extraction mixed solution, concentratedly obtains crude product and obtains pure product through column chromatography for separation.Productive rate: 80%.
1H?NMR(400MHz,CDCl
3,298K):δ(ppm)＝7.91-7.96(dd,J＝8.0Hz,2H),8.26-8.31(d,J＝8.0Hz,2H),8.71(d,J＝2.0Hz,2H)。
4. the preparation of function C^N part:
Adopt the synthetic corresponding C^N part of Suzuki method, preparation method: under nitrogen protection, by bromo-derivative (1mmol) with boronic acid compounds (1mmol) taking four (triphenyl phosphorus) palladium as catalyzer is at toluene/ethanol/K
2cO
3in saturated solution (1:2:1, v:v), back flow reaction is spent the night, and organic phase is collected in extraction, column chromatography, and bromo-derivative and boronic acid compounds are as follows
5. when C^N part is
time, the preparation of iridium dichloro bridge
Take 2-phenylquinoline (2.5mmol) and IrCl
33H
2o (1mmol) mixes in input three-necked bottle, and vacuumize on biexhaust pipe-Bao nitrogen-vacuumize, moves in circles three times, finally adopts the whole reaction system of nitrogen protection.The ethylene glycol ethyl ether that is 3:1 by volume ratio and the mixture of water are injected in reaction system, are warming up to 110 DEG C, magnetic agitation reaction 24 hours.After reaction finishes, system is cooled to room temperature, filtering-depositing, and with ethanol and washing, the solid product obtaining is iridium dichloro bridge, can directly drop into next step reaction.
6. the preparation of complex of iridium intermediate
Take C^N cyclic metal complexes iridium dichloro bridge (1mmol), 5; 5'-bis-is bromo-2, and 2'-dipyridyl (2.3mmol) is added in three-necked bottle, vacuumize on biexhaust pipe-Bao nitrogen-vacuumize; move in circles three times, finally adopt the whole reaction system of nitrogen protection.In the mixture injection system of the methylene dichloride that is 2:1 by volume ratio and methyl alcohol, temperature is risen to 50 DEG C, stirring and refluxing.React after 5 hours, add the Potassium Hexafluorophosphate solid of 0.72mmol, continue stirring at room temperature, react 1 hour.Reaction finishes rear concentrated purification, finally uses methylene dichloride and normal hexane recrystallization, obtains solid product and is complex of iridium intermediate.Productive rate: 80%.
1h NMR (400MHz, CDCl
3, 298K): δ (ppm)=6.49-6.54 (d, J=8.0Hz, 2H), 6.82-6.88 (t, J=7.4Hz, 2H), 7.06-7.17 (t, J=8.0Hz, 2H), 7.14-7.22 (t, J=8.0Hz, 4H), 7.38-7.45 (t, J=8.0Hz, 2H), 7.75 (d, J=7.6Hz, 2H), (8.00-8.08 t, J=12.0Hz, 4H), 8.11 (s, 2H), 8.17-8.28 (m, 6H) .MS (MALDI-TOF): m/e[M-PF
6]
+theoretical value 915.01, experimental value 915.65.
7. the preparation of complex of iridium end product
In round-bottomed flask, add complex of iridium intermediate (2.0mmol) and p-methylphenyl anthracene pinacol boric acid ester (5.0mmol), 80 DEG C of confined reactions 12 hours in the mixed solution of 20mL ethanol/toluene/salt of wormwood saturated aqueous solution (v:v1:2:1), reaction stops rear standing cooling, collect organic phase with dichloromethane extraction mixed solution, concentrated obtain crude product and obtain pure complex of iridium end product through column chromatography for separation.Productive rate: 60%.
1H?NMR(400MHz,CDCl
3,298K):δ(ppm)＝2.55(d,J＝11.2Hz,6H),6.52-6.59(m,2H),6.60-6.67(m,1H),6.78(t,J＝8.0Hz,2H),7.15-7.23(m,3H),7.27-7.31(m,4H),7.32-7.39(m,4H),7.42-7.49(t,J＝12.0Hz,6H),7.50-7.60(m,7H),7.61-7.65(m,2H),7.68-7.82(m,4H),7.88-7.95(m,2H),7.98(t,J＝4.0Hz,2H),8.06-8.15(m,2H),8.25-8.44(m,3H),8.64(dd,J＝8.0Hz,1H),8.74-8.83(m,2H)。MS (MALDI-TOF): m/e[M-PF
6]
+theoretical value 1291.42, experimental value 1292.29.
Use gas meter to keep general gas flow constant, change the ratio of nitrogen, oxygen, the weary oxygen that carries out the title complex in the present embodiment detects.Fig. 1 has provided the title complex in the present embodiment at CH
3the emmission spectrum changing with oxygen partial pressure in CN solution, as shown in the figure, oxygen partial pressure is within the scope of 0-20%, along with the reduction gradually of oxygen partial pressure, the phosphorescent emissions intensity enhancing of the title complex in the present embodiment 11.1 times, it can be said that the title complex in bright the present embodiment can be realized oxygen sensing preferably.
KB cell is applied to hatch respectively 60 minutes under 37 DEG C of conditions after and carries out co-focusing imaging with the DMSO solution of the Complex probe in 20 μ M embodiment 1.As shown in Figure 2, control group before weary oxygen is tested under air conditions, it after weary oxygen, is the experimental group under condition of nitrogen gas, from the contrast of two groups of images, can find out, the intensity of the cell phosphorescent emissions of the control group under the strength ratio air conditions of the cell phosphorescent emissions of the experimental value after weary oxygen obviously strengthens, instrument draw experimental group than the phosphorescent emissions intensity enhancing of control group 3.6 times, experimental result shows that the Complex probe in the present embodiment can realize intracellular oxygen sensing preferably.
Life-span to the Complex probe in embodiment 1 before and after weary oxygen has also been carried out fluorescence lifetime imaging research.As shown in Figure 3, the phosphorescent lifetime of the control group under the air conditions of the phosphorescent lifetime of the experimental group after weary oxygen before than weary oxygen obviously strengthens.In addition, Fig. 4 has also provided time gate image, control group before weary oxygen phosphorescent emissions after 250ns is just very weak, and the phosphorescent emissions of the experimental group after weary oxygen still keeps certain intensity after 250ns, and the Complex probe further illustrating in the present embodiment has good oxygen sensing capabilities.
More than describe preferred embodiment of the present invention in detail.The ordinary skill that should be appreciated that this area just can design according to the present invention be made many modifications and variations without creative work.Therefore, all technician in the art, all should be in by the determined protection domain of the claims in the present invention book under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (4)
1. a phosphorescent iridium complex, is characterized in that the complex of iridium being made up of the assistant ligand of cyclic metal complexes, metal center and phenmethyl replacement anthracene has following structural formula:
Wherein, C^N part is the one in lower array structure:
2. the preparation method by phosphorescent iridium complex as claimed in claim 1, is characterized in that this preparation method's synthetic route is as follows:
Step 1. under nitrogen protection, in the reaction solution system of ethanol/toluene/salt of wormwood saturated aqueous solution (v:v1:2:1), add methylphenylboronic acid and 9,10-dibromoanthracene, under the catalysis of four (triphenyl phosphorus) palladium, react 12 hours, reaction stops rear standing cooling, collect organic phase with dichloromethane extraction mixed solution, concentrated obtain crude product and obtain the bromo-10-p-methylphenyl of pure product: 9-anthracene through column chromatography for separation;
Step 2 .1, the two Diphenyl phosphino ferrocene palladium chlorides of 1'-are as catalyzer, 9-bromo-10-p-methylphenyl anthracene and duplex pinacol boric acid ester 80 DEG C of nitrogen protection confined reactions 12 hours in the alkaline environment of dioxane, salt of wormwood, reaction stops first dioxane being steamed and being removed afterwards, then use dichloromethane extraction mixed solution, collect organic phase, concentrate and obtain crude product, obtain pure target product through column chromatography for separation: p-methylphenyl anthracene pinacol boric acid ester;
Step 3. make solvent with m-xylene, 2,5-dibromo pyridine reacts with normal-butyl tin, taking four (triphenyl phosphorus) palladium as catalyzer, 130 DEG C of reactions of lucifuge three days, add disodium EDTA to remove remaining tin reagent after reaction finishes, by dichloromethane extraction mixed solution collection organic phase, concentrated obtain crude product to obtain pure product: 5,5'-bis-through column chromatography for separation bromo-2,2'-dipyridyl;
Step 4. under nitrogen protection, by the N^N part of iridium dichloro bridge and dipyridyl 40 DEG C of confined reactions 4 hours in methylene chloride/methanol (2:1, v:v) mixed solution, add Potassium Hexafluorophosphate to continue reaction 1 hour after being cooled to room temperature, separating-purifying, obtains complex of iridium intermediate;
Step 5. under nitrogen protection; in the reaction solution system of ethanol/toluene/salt of wormwood saturated aqueous solution (v:v1:2:1), add p-methylphenyl anthracene pinacol boric acid ester and complex of iridium intermediate; under the catalysis of four (triphenyl phosphorus) palladium, react 12 hours; reaction stops rear standing cooling; collect organic phase with dichloromethane extraction mixed solution, concentrated obtain crude product and obtain pure complex of iridium end product through column chromatography for separation.
3. a phosphorescent iridium complex as claimed in claim 1, is characterized in that this phosphorescent iridium complex is applied to weary oxygen and detects.
4. a phosphorescent iridium complex probe as claimed in claim 1, is characterized in that this phosphorescent iridium complex is applied to cell marking and bio-imaging.
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| CN105294771A (en) * | 2015-09-16 | 2016-02-03 | 南京邮电大学 | Anionic type iridium complex for oxygen sensing, and preparation method and application thereof |
| CN107340278A (en) * | 2017-06-06 | 2017-11-10 | 北京福纳康生物技术有限公司 | Method based on fullerene or derivatives thereof using fluorescent molecular probe detection oxygen |
| CN107417737A (en) * | 2017-08-04 | 2017-12-01 | 南京邮电大学 | A kind of ionic type iridium complex with double phosphorescent emissions properties and its preparation method and application |
| CN108948093A (en) * | 2018-07-12 | 2018-12-07 | 南京邮电大学 | Phosphorescent metal complex of iridium and the preparation method and application thereof with singlet oxygen detection effect |
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| CN107340278B (en) * | 2017-06-06 | 2020-01-21 | 北京福纳康生物技术有限公司 | Method for detecting oxygen by adopting fluorescent molecular probe based on fullerene or fullerene derivative |
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| CN108948093A (en) * | 2018-07-12 | 2018-12-07 | 南京邮电大学 | Phosphorescent metal complex of iridium and the preparation method and application thereof with singlet oxygen detection effect |
| CN108948093B (en) * | 2018-07-12 | 2020-10-02 | 南京邮电大学 | Phosphorescent metal iridium complex with singlet oxygen detection effect and preparation method and application thereof |
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