CN106243154A - A kind of phosphorescent iridium complex probe of cell membrane targeting and its preparation method and application - Google Patents
A kind of phosphorescent iridium complex probe of cell membrane targeting and its preparation method and application Download PDFInfo
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- CN106243154A CN106243154A CN201610618705.9A CN201610618705A CN106243154A CN 106243154 A CN106243154 A CN 106243154A CN 201610618705 A CN201610618705 A CN 201610618705A CN 106243154 A CN106243154 A CN 106243154A
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 77
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000000523 sample Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 210000000170 cell membrane Anatomy 0.000 title claims abstract description 21
- 230000008685 targeting Effects 0.000 title claims abstract description 18
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 210000004027 cell Anatomy 0.000 claims abstract description 19
- 238000001514 detection method Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 8
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000003384 imaging method Methods 0.000 abstract description 10
- 239000003446 ligand Substances 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 239000000090 biomarker Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 14
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002189 fluorescence spectrum Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- -1 hydroxyl radical free radical Chemical class 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- 206010061218 Inflammation Diseases 0.000 description 2
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 2
- 102000003896 Myeloperoxidases Human genes 0.000 description 2
- 108090000235 Myeloperoxidases Proteins 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000012531 culture fluid Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000004054 inflammatory process Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 210000003739 neck Anatomy 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003254 radicals Chemical group 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 0 *[n]1c(-c2ccccc2)nc2c1cccc2 Chemical compound *[n]1c(-c2ccccc2)nc2c1cccc2 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 208000037273 Pathologic Processes Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000030833 cell death Effects 0.000 description 1
- MAYPHUUCLRDEAZ-UHFFFAOYSA-N chlorine peroxide Inorganic materials ClOOCl MAYPHUUCLRDEAZ-UHFFFAOYSA-N 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000003412 degenerative effect Effects 0.000 description 1
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000012678 infectious agent Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 210000000265 leukocyte Anatomy 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000002438 mitochondrial effect Effects 0.000 description 1
- 230000036542 oxidative stress Effects 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 230000009054 pathological process Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 238000004313 potentiometry Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 206010039073 rheumatoid arthritis Diseases 0.000 description 1
- 230000036259 sexual stimuli Effects 0.000 description 1
- 230000019491 signal transduction Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 210000001082 somatic cell Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000759 toxicological effect Toxicity 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002676 xenobiotic agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Immunology (AREA)
- Analytical Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Molecular Biology (AREA)
- Biomedical Technology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention belongs to organic photoelectric functional material technical field, it is provided that phosphorescent iridium complex probe of a kind of cell membrane targeting and its preparation method and application.Such coordination compound is made up of N^N assistant ligand, metal center and the C^N cyclic metal complexes containing long alkyl chain, and general structure is shown below, and the N^N assistant ligand of described phosphorescent iridium complex probe rolls into a ball C=N OH containing oximido；Containing long alkyl chain on C^N cyclic metal complexes.This phosphorescent iridium complex probe has extraordinary application prospect in hypochlorite detection, cell imaging and biomarker.The preparation method of described complex of iridium is simple, mild condition；As phosphorescence probe, at ClO‑In the presence of phosphorescent emissions be obviously enhanced, Detection results is notable, to ClO‑There is high selectivity, and respond fast, there is low bio-toxicity, and be easily accessible in cell membrane so that this kind of probe can be used for cell membrane targeting ClO‑Detection.
Description
Technical field
The invention belongs to organic photoelectric functional material technical field, be specifically related to a kind of cell membrane targeting containing long alkyl chain
Phosphorescent iridium complex probe and preparation method thereof and application in hypochlorite detection, cell imaging and biomarker.
Background technology
It is a series of that active oxygen (Reactive oxygen species, ROS) refers to that molecular oxygen produces in reduction process
Intermediate product, including existing with radical form and with what radical form existed, not there is highly active intermediate product, including
Have ultra-oxygen anion free radical, hydroxyl radical free radical, peroxy radical, alkoxy free group, hypochlorous acid, hydrogen peroxide, singlet oxygen,
Both peroxyl radical.Oxygen molecule is the required material in organism metabolic process, and the ROS in organism is mainly by these
Oxygen molecule is produced by series of chemical.
Molecular oxygen is the required component that all oxygen consumption organisms maintain its vital movement.Active oxygen species ROS in human body
The oxygen mainly produced by mitochondrial respiratory process, simultaneously, it is possible to by generating, such as in external disturbance induction organism
Xenobiotics, infectious agent and ultraviolet.ROS participates in physiology and pathological process widely, such as signal transduction, inflammation, cancer
Become and nervous tissue's degenerative damage.Although producing ROS in normal cellular environment is necessary for life, but when it
Under external source sexual stimulus generate excess time, organism is also had harm.The ROS of excess is drawn by the oxidation of biomolecule
The oxidative stress risen, such as, the Oxidation of lipid, protein and DNA, and inducing cell death.
ROS regulates various physiological process.Hypochlorous acid (HOCl), the active oxygen of a biological significance, is to live
Change in leukocyte, produced by myeloperoxidase (MPer) catalysis chlorine peroxide ion.In defence naturally, hypochlorous acid is also a kind of weight
The antibacterial wanted.But, the disease that the exception of hypochlorous acid level is relevant to many inflammation has close contacting, including cardiovascular
Disease, the damage of human erythrocyte, pneumonopathy, rheumatoid arthritis and cancer.So, hypochlorous detection is very important.
At present, many detect hypochlorous method, such as, electrolysis, potentiometric method, spectrophotography being had been developed, chemiluminescence is examined
Survey.WeiyingLin has been combined into a kind of detection ClO-Ratio fluorescent probe, when acting on analyte, fluorescent emission ratio
Rate (I509/I439) can increase to 2.74 from 0.28, and have higher selectivity (Chem.Eur.J., 2009,15,2305
2309).Chen Zhong rather organizes with the 2 of oximate, and 2 '-bipyridyl selectivity goes to detect hypochlorous acid, compared to other active oxygen and metal
Ion has higher susceptiveness (Analyst, 2011,136,2277 2282).This probe is detection based on fluorescence signal.
Compared to fluorescence signal, phosphorescent signal detection have the advantage that there is big Stokes displacement, visible ray swashs
Send out, good light stability, long emission lifetime, high quantum efficiency and launch wavelength easily regulation etc..The biggest stoke
This displacement can be easily discriminated and excite and launch, long emission lifetime up time resolution techniques and background fluorescence signal phase
Distinguish signal to noise ratio and sensitivity to improve detection and visible ray can be used to carry out exciting reduction photobleaching.Therefore, exploitation tool
Selectively, the phosphorescence probe that can be used for living body detection is significant.
Summary of the invention
In view of prior art exists above-mentioned technical problem, it is an object of the invention to provide the phosphorus of a class cell membrane targeting
Light complex of iridium probe, provides their preparation method, and proposes this kind of Complex probe at hypochlorite detection, cell imaging
And the application in biomarker.The technical solution used in the present invention is as described below:
The present invention provides the phosphorescent iridium complex probe of a kind of cell membrane targeting, it is characterised in that described phosphorescent iridium coordinates
Containing oximido group (-C=N-OH) on the N^N assistant ligand of physical prospecting pin, containing long alkyl chain, described phosphorescence on cyclic metal complexes
Complex of iridium probe has a following structural formula formula:
Wherein, n is 6,12 or 18, and N^N assistant ligand is the one in following structure:
Above-mentioned phosphorescent iridium complex probe can be used to selective enumeration method hypochlorite.Containing long alkane on its cyclic metal complexes
Base chain, it is achieved cell membrane targeting；Containing oximido group (C=N-OH) on its N^N assistant ligand, when adding liquor natrii hypochloritis,
Oximido group (C=N-OH) is oxidized to carboxyl (COOH), and complex of iridium is luminous, it is achieved that the open-type of phosphorescence probe, thus
There is good application prospect in cell imaging field.
The present invention also provides for the preparation method of the complex of iridium of above-mentioned cell membrane targeting phosphorescent emissions, it is characterised in that
Concretely comprising the following steps of described preparation method:
(1) preparation of iridium dichloro bridge: (described N^N part is selected from above-mentioned N^N by the N^N part containing oximido (C=N-OH)
One in structure) join in the mixed solution of ethylene glycol and water under inert gas shielding with iridous chloride, heating
Stirring, prepares dichloro bridge intermediate；
(2) preparation of complex of iridium intermediate: iridium dichloro bridge intermediate and the C^N ring gold containing long alkyl chain that will obtain
Metal ligand 50 DEG C of confined reaction 5h under inert gas shielding in dichloromethane and methyl alcohol mixed liquor, reaction is cooled to room after terminating
Temperature, obtains complex of iridium intermediate；The general structure of described C^N cyclic metal complexes is:
(3) preparation of complex of iridium probe: add Potassium Hexafluorophosphate in the reactant liquor after step (2) reaction terminates and continue
After reaction 8h, the complex of iridium probe that separating-purifying obtains.
One feasible synthetic route of preparation method of the present invention is (to be only in preparation method of the present invention
Individual embodiment, does not represent all technical schemes that the present invention comprises):
Phosphorescence heavy metal iridium complex has a photophysical property well, the longest emission lifetime, the most photochemical
Learn triplet state photo-quantum efficiency high under stability, room temperature, the transmitting wavelength easily regulated, big Stokes shift and visible ray
The advantages such as district excites, currently, have been applied to the field such as electroluminescent and luminescent electrochemical cell device, bio-sensing.Relative to
Small molecule organic fluorescent dye molecule, the emission lifetime up time resolution techniques of phosphorescence heavy metal complex length is glimmering with background
Optical signal distinguishes the sensitivity to improve detection and signal to noise ratio mutually.Complex of iridium probe of the present invention has well application
Prospect, especially in biological cell detection and imaging field.
The phosphorescent iridium complex probe of cell membrane targeting of the present invention can be applicable to hypochlorite detection.
Above-mentioned complex of iridium probe is dissolved in CH3OH/H2In O (v/v, 2:1) mixed solution, gradually it is added drop-wise to ClO-'s
CH3OH/H2In O mixed solution, drip ClO every time-Rear all heated and stirred are so that ClO-Fully react with above-mentioned complex of iridium, and
Test its fluorescence emission spectrum.By analysis of fluorescence emission spectrum it will be seen that be near 600nm at optical wavelength, above-mentioned iridium
The luminescence of complex solution own is the most weak, along with ClO-Addition, the fluorescence spectrum of complex of iridium solution there occurs change at once, companion
Along with ClO-The rising of dropping concentration, the fluorescence spectrum generation blue shift of complex of iridium and fluorescence intensity gradually rise.Work as ClO-Drip
Adding concentration equivalent when reaching 30eq., titration reaches terminal, is further continued for dripping ClO-, spectrum the most no longer changes.
Visible complex of iridium probe of the present invention to the response of hypochlorite clearly, has the sensitiveest
Degree and the lowest detection minimum.This is because above-mentioned complex of iridium probe itself only has the lowest fluorescent effect, but, secondary
Under the strong oxidation of chlorate anions, the group containing oximido (-C=N-OH) on above-mentioned complex of iridium probe be oxidized to carboxyl (-
COOH), generating a kind of new complex of iridium, this complex of iridium has the strongest fluorescent effect.Then, even if the most little is secondary
Chlorate anions, under the contrast of fluorescent effect, is also readily available obvious testing result.
It is dissolved in CH at above-mentioned complex of iridium probe3OH/H2O (v/v, 2:1) mixed solution is separately added into excess
NaClO3、CuCl2、LiClO3、AlCl3、MgCl2、Na2CO3、Na2SO4、NaOAc、ZnCl2、H2O2、NaNO2, NaClO solution, point
Do not survey its emission spectrum.By contrast, the intensity of emission spectrum is all had no significant effect by other ions with launching wavelength,
I.e. complex of iridium probe is to ClO-There is preferable selectivity.
In summary, the phosphorescent iridium complex probe of cell membrane targeting of the present invention can be applicable to hypochlorite inspection
Surveying, this is to further investigation ClO-Physiology and toxicological effect in organisms are significant.
The phosphorescent iridium complex probe of cell membrane targeting of the present invention applies also for cell imaging and biomarker.
Cultured two groups of Hela cells, one of which is hatched with described complex of iridium solution, and is washed 3 with culture fluid
Secondary, as blank group；Another group complex of iridium is hatched, and drips ClO-Solution, and wash 3 times by culture medium, as
Experimental group.Using Laser Scanning Confocal Microscope to take pictures two groups of cells, the photo contrasting two groups of cells is visible, base on cellular control unit film
Originally there is no fluorescent emission, and in experimental group cell membrane, have stronger phosphorescent emissions.
It addition, the fluorescent effect that described complex of iridium and the iridium that obtains after being aoxidized by hypochlorite coordinate all can use visible
Light excites, and can avoid using the potential photic damage to living body biological cell of the burst of ultraviolel light source, the most beneficially probe application
Photoimaging mensuration, cell imaging and biomarker field in the hypochlorite of active somatic cell targeting.
There is advantages that 1, complex of iridium of the present invention is used as phosphorescence probe, at ClO-In the presence of
Phosphorescent emissions is obviously enhanced, and Detection results is notable；2, phosphorescence probe material of the present invention is to ClO-There is high selectivity,
And respond fast；3, this probe material has low bio-toxicity, and is easily accessible in cell membrane so that this kind of probe can be used for carefully
After birth targeting ClO-Detection, cell imaging and biomarker field；4, the preparation method of described complex of iridium is simple, mild condition
Accompanying drawing explanation
Fig. 1. the ultraviolet visible absorption spectra figure of the coordination compound Ir-1 of embodiment 1 synthesis in the present invention.
Fig. 2. the fluorescent emission titration spectrogram of the coordination compound Ir-2 of the 2-in-1 one-tenth of embodiment in the present invention.
Fig. 3. the MALDI-TOF spectrogram of the coordination compound Ir-2 of the 2-in-1 one-tenth of embodiment in the present invention.
Fig. 4. the cell imaging figure of the coordination compound Ir-2 of the 2-in-1 one-tenth of embodiment in the present invention.
Detailed description of the invention
In order to be more fully understood that the content of patent of the present invention, further illustrate the present invention's below by concrete example
Technical scheme.But these embodiments are not limiting as the present invention.Embodiment 1: the preparation of coordination compound Ir-1:
N^N assistant ligand in the present embodiment be C=N-OH-bpy, C^N cyclic metal complexes be the long-chain with 12 carbon
The C-12 of alkyl, both structural formulas are respectively as follows:
The synthetic reaction formula of the present embodiment is:
(1) preparation of iridium dichloro bridge: weigh N^N assistant ligand C=N-OH-bpy (2.2mmol) and IrCl3·3H2O
(1mmol), during mixing puts into three-necked bottle, on biexhaust pipe, evacuation-guarantor's nitrogen-evacuation, moves in circles three times, finally uses
Nitrogen protects whole reaction system.The mixture of ethylene glycol that volume ratio is 3:1 and water is injected in reaction system, rises
Temperature is to 110 DEG C, and magnetic agitation is reacted 24 hours.After reaction terminates, system is cooled to room temperature, filters precipitation, and with ethanol with
Washing, the solid product obtained is iridium dichloro bridge, can direct plunge into next step reaction.
(2) preparation of complex of iridium intermediate: weigh iridium dichloro bridge (1mmol) again, C-12 (2.4mmol) adds to three necks
In Ping, on biexhaust pipe, evacuation-guarantor's nitrogen-evacuation, moves in circles three times, finally uses nitrogen to protect whole reactant
System.By in the mixture injection system of dichloromethane that volume ratio is 2:1 and methanol, temperature is risen to 50 DEG C, is stirred at reflux.
(3) preparation of complex of iridium probe: after reacting 5 hours, adds the Potassium Hexafluorophosphate solid of 0.75mmol, continues to stir
Mix reaction 8h.Reaction concentrates after terminating and purifies, and finally with dichloromethane and normal hexane recrystallization, obtains solid product and is iridium and joins
Compound Ir-1.Productivity: 69%.1H NMR (400MHz DMSO): δ=7.90 (d, J=5.6Hz, 1H), 7.73 (d, J=
8.0Hz, 2H), 7.40 (m, 2H), 7.28 (d, t, J=3.2Hz, 7.6Hz, 2H), 6.33-6.28 (m, 2H), 5.77-5.70 (m,
2H),4.71-4.58(m,4H),2.08-1.95(m,4H),1.82-1.65(m,4H),1.52-1.43(m,4H),1.29-1.17
(m, 32H), 0.87 (t, J=6.8Hz, 6H)；[m/e] (M, MALDI-TOF) theoretical value: 1128.56, experiment value: 1128.79.
Embodiment 2: the preparation of coordination compound Ir-2:
N^N assistant ligand in the present embodiment be C=N-OH-bpy, C^N cyclic metal complexes be the long-chain with 18 carbon
The structural formula of the C-18 of alkyl, C-18 is:
The synthetic reaction formula of the present embodiment is:
(1) preparation of iridium dichloro bridge: weigh N^N assistant ligand C=N-OH-bpy (2.2mmol) and IrCl3·3H2O
(1mmol), during mixing puts into three-necked bottle, on biexhaust pipe, evacuation-guarantor's nitrogen-evacuation, moves in circles three times, finally uses
Nitrogen protects whole reaction system.The mixture of ethylene glycol that volume ratio is 3:1 and water is injected in reaction system, rises
Temperature is to 110 DEG C, and magnetic agitation is reacted 24 hours.After reaction terminates, system is cooled to room temperature, filters precipitation, and with ethanol with
Washing, the solid product obtained is iridium dichloro bridge, can direct plunge into next step reaction.
(2) preparation of complex of iridium intermediate: weigh iridium dichloro bridge (1mmol) again, C-18 (2.4mmol) adds to three necks
In Ping, on biexhaust pipe, evacuation-guarantor's nitrogen-evacuation, moves in circles three times, finally uses nitrogen to protect whole reactant
System.By in the mixture injection system of dichloromethane that volume ratio is 2:1 and methanol, temperature is risen to 50 DEG C, is stirred at reflux.
(3) preparation of complex of iridium probe: after reacting 5 hours, adds the Potassium Hexafluorophosphate solid of 0.75mmol, continues to stir
Mix reaction 8h.Reaction concentrates after terminating and purifies, finally with dichloromethane and normal hexane recrystallization, finally with dichloromethane and just own
Alkane recrystallization, obtains solid product and is complex of iridium Ir-2.Productivity: 75%.1H NMR(400MHz DMSO):8.23-8.19
(m,2H),7.96-7.90(m,4H),7.72-7.68(m,2H),7.41-7.39(m,1H),7.20-7.13(m,4H),6.40
(d, J=6.0Hz, 2H), 3.95-3.88 (m, 4H), 1.40-1.20 (m, 2H), 0.89 (t, J=7.2Hz, 6H)；[m/e](M,
MALDI-TOF) theoretical value: 1296.89, experiment value: 1296.752.
Embodiment 3: ultraviolet visible absorption spectra figure
Complex of iridium Ir-1 is dissolved in CH3OH/H2The absorption spectrogram surveyed in O (v/v, 2:1) mixed solution, result such as Fig. 1
Shown in, as shown in Figure 1, its maximum absorption wavelength is at about 225nm.
Embodiment 4: the emission spectrum of probe I r-2 is to ClO-Response:
Complex of iridium Ir-2 is dissolved in CH3OH/H2In O (v/v, 2:1) mixed solution, gradually add ClO-CH3OH/
H2In O mixed solution, drip ClO every time-After, in 37 DEG C of waters bath with thermostatic control, heated and stirred 5 minutes, make ClO-With complex of iridium Ir-
2 fully react, and test its fluorescence emission spectrum subsequently, as shown in Figure 2.At 601nm, complex of iridium Ir-2 solution itself is luminous
The most weak, along with ClO-Addition, the fluorescence spectrum of complex of iridium Ir-2 solution there occurs change, at once along with ClO-Drip dense
The rising of degree, the fluorescence spectrum blue shift of complex of iridium Ir-2 the fluorescence intensity at 595nm gradually rise.Work as ClO-Dropping
When concentration equivalent reaches 30eq., titration reaches terminal, is further continued for dripping ClO-, spectrum the most no longer changes.
Embodiment 5: probe I r-2 is in the solution to ClO-Selectivity experiment:
Prepare the complex solution (CH of 1.5 μMs3OH/H2O (v/v, 2:1), pipettes the joined compound solution of 2.5mL in colorimetric
In ware, add the NaClO of excess3、CuCl2、LiClO3、AlCl3、MgCl2、Na2CO3、Na2SO4、NaOAc、ZnCl2、H2O2、
NaNO2, NaClO solution, survey its emission spectrum respectively.Other ions all have no significant effect.Experimental data shows: material is to ClO-
There is preferable selectivity.
Embodiment 6: living cells imaging experiment:
Hela cell is cultivated according to American Type Tissue Culture Collection regulation.Hela
Cell is hatched 30 minutes with 1.5 μMs of complex of iridium Ir-2 solution at 37 DEG C, washs 3 times with culture fluid, as blank group
Laser Scanning Confocal Microscope photographic result as shown in Figure 4, cell membrane does not has fluorescent emission substantially；Experimental group is used at Hela cell
After 1.5 μMs of complex of iridium Ir-2 hatch 30 minutes under the conditions of 37 DEG C, then use 1.5ClO-Take pictures under solution focusing microscope, afterwards
Wash 3 times by culture medium, be placed under Laser Scanning Confocal Microscope and take pictures, have stronger phosphorescent emissions in photo display cell membrane, knot
Fruit is as shown in Figure 4.This test result indicate that, complex of iridium Ir-2 can be used for detecting the ClO in living cells-。
Claims (4)
1. the phosphorescent iridium complex probe of a cell membrane targeting, it is characterised in that the N^N of described phosphorescent iridium complex probe is auxiliary
Help and roll into a ball C=N-OH containing oximido on part；Containing long alkyl chain on cyclic metal complexes；This complex of iridium has following structure and leads to
Formula:
Wherein n is 6,12 or 18；Wherein, N^N part one in following structure:
2. the preparation method of the phosphorescent iridium complex probe of a cell membrane targeting as claimed in claim 1, it is characterised in that
Concretely comprising the following steps of described preparation method:
(1) preparation of iridium dichloro bridge: by the one in the above-mentioned N^N part containing oximido with iridous chloride in inert gas shielding
Under join in the mixed solution of ethylene glycol and water, heated and stirred, prepare dichloro bridge intermediate；
(2) preparation of complex of iridium intermediate: the iridium dichloro bridge intermediate obtained is joined with the C^N ring metal containing long alkyl chain
Body 50 DEG C of confined reaction 5h under inert gas shielding in dichloromethane and methyl alcohol mixed liquor, reaction is cooled to room temperature after terminating,
Obtain complex of iridium intermediate；The general structure of described C^N cyclic metal complexes is:
(3) preparation of complex of iridium probe: add Potassium Hexafluorophosphate in the reactant liquor after step (2) reaction terminates and continue reaction
After 8h, the complex of iridium probe that separating-purifying obtains.
3. the phosphorescent iridium complex probe of an a kind of cell membrane targeting as claimed in claim 1, it is characterised in that this phosphorescence
Complex of iridium is applied to hypochlorite detection.
4. the phosphorescent iridium complex probe application of an a kind of cell membrane targeting as claimed in claim 1 in cell marking with become
Picture.
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