CN106749421B - The preparation and its application of highly sensitive singlet oxygen phosphorescence probe - Google Patents
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000000523 sample Substances 0.000 title claims description 28
- 238000002360 preparation method Methods 0.000 title abstract description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- 150000001768 cations Chemical class 0.000 claims 2
- 230000007935 neutral effect Effects 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 16
- 230000035945 sensitivity Effects 0.000 abstract description 9
- 239000012736 aqueous medium Substances 0.000 abstract 1
- 238000001514 detection method Methods 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
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- OALHHIHQOFIMEF-UHFFFAOYSA-N 3',6'-dihydroxy-2',4',5',7'-tetraiodo-3h-spiro[2-benzofuran-1,9'-xanthene]-3-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 OALHHIHQOFIMEF-UHFFFAOYSA-N 0.000 description 1
- FCNCGHJSNVOIKE-UHFFFAOYSA-N 9,10-diphenylanthracene Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 FCNCGHJSNVOIKE-UHFFFAOYSA-N 0.000 description 1
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- 229910052771 Terbium Inorganic materials 0.000 description 1
- XQAXGZLFSSPBMK-UHFFFAOYSA-M [7-(dimethylamino)phenothiazin-3-ylidene]-dimethylazanium;chloride;trihydrate Chemical compound O.O.O.[Cl-].C1=CC(=[N+](C)C)C=C2SC3=CC(N(C)C)=CC=C3N=C21 XQAXGZLFSSPBMK-UHFFFAOYSA-M 0.000 description 1
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- MWPLVEDNUUSJAV-LSMJWXKXSA-N anthracene Chemical group [13CH]1=[13CH][13CH]=[13CH][13C]2=CC3=CC=CC=C3C=[13C]21 MWPLVEDNUUSJAV-LSMJWXKXSA-N 0.000 description 1
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
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- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
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- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical class [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 201000000585 muscular atrophy Diseases 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000018343 nutrient deficiency Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 230000004792 oxidative damage Effects 0.000 description 1
- 230000007170 pathology Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 238000005539 phosphorimetry Methods 0.000 description 1
- 230000000258 photobiological effect Effects 0.000 description 1
- 231100000589 photocarcinogenesis Toxicity 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical class [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 230000008685 targeting Effects 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000001845 vibrational spectrum Methods 0.000 description 1
Classifications
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- 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
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- 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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- 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)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses the applications in terms of the preparation method of binuclear ruthenium and its singlet oxygen sensor.Using the logarithm of the concentration of singlet oxygen as abscissa, the logarithm of luminous intensity is that ordinate draws out standard working curve, for measuring singlet oxygen concentration in neutral and alkaline aqueous medium.This method has the advantages that excited by visible light, high sensitivity, highly selective and easy-operating.
Description
Technical field
The present invention relates to singlet oxygen in solution (1O2) measurement, it is specifically a kind of to contain anthracycline derivatives ligand
A kind of preparation and its application of double-core ruthenium metal complex singlet oxygen phosphorescence probe.
Background technique
Singlet oxygen is a kind of unstable existence form that oxygen molecule is in high energy excitation state, and singlet oxygen is as organic
A kind of preciousness reagent in chemistry, in many photochemistry and optical-biological reaction, as light degradation, the light conversion of pollutant, chemiluminescence,
During organism deterioration by oxidation, even photocarcinogenesis etc., highly important role all play.In organic synthesis,
Singlet oxygen makes the introducing oxygen in the single-minded organic compound of High level of stereoselectivity become extremely to be easy.In biosystem, single line
State oxygen has great influence to life system, and the physiology oxidation of singlet is increasingly interested by researchers.It is single
Line state oxygen plays an important role in cellular damage and apoptosis, it may cause the strong oxidizing property damage to body, to draw
The generation for playing body lipid peroxidation, leads to the damage of biomembrane, parteriole, DNA, protein and central nervous system,
Accelerate the aging and death of body, therefore be considered as toxicity species important in vivo, causes disease related with oxidative damage,
Such as cataract, pulmonary edema, diabetes, muscular atrophy, nutritional deficiency, mental disease and tumour germinating [(a) K.Briviba,
L.O.Klotz,H.Sies,Toxic and signaling effects of photochemically or chemically
generated singlet oxygen in biological systems,Biol.Chem.,1997,378,1259.b)
J.R.Wagner,P.A.Motchnik,R.Stocker,H.Sies,B.N.Ames,The oxidation of blood
plasma and low density lipoprotein components by chemically generated singlet
oxygen,J.Biol.Chem.,1993,268,18502.].Singlet oxygen is in the regulation such as the hyperplasia of cell, differentiation, apoptosis
It plays an important role, it is considered to be a kind of new second messenger [(a) R.W.Redmond, I.E.Kochevar, Spatially
resolved cellular responses to singlet oxygen,Photochem.Photobiol.,2006,82
(5),1178-1186.(b)N.L.Oleinick,R.L.Morris,I.Belichenko,The role of apoptosis
in response to photodynamic therapy:what,where,why,and how,
Photochem.Photobiol.Sci.,2002,1,1–21.].On the contrary, people also can use the strong oxidizing property of singlet oxygen
Matter goes to kill malignant cell or tissue, achievees the purpose that cure cancer.Experiment discovery, when malignant cell obtains and ties
When the ability of conjunction singlet oxygen sensitizers drug is noticeably greater than normal tissue, after illumination, the singlet of drug molecule generation
Oxygen can selectively kill tumour cell.Medically with the singlet oxygen that the photosensitive method of methylene blue generates come to Plasma disinfection and
The photodynamic diagnosis of tumour, before this photodynamic therapy technology has a wide range of applications in the diagnosing and treating of tumour
Scape.Singlet oxygen and human health and disease are closely related, are the hot spots of current life science and chemical science crossing research.
Since singlet oxygen has such consequence during photochemistry and photo-biological,1O2Detection receives much attention,
Especially in biosystem1O2Detection increasingly cause the concern of researcher.Research and develop list highly sensitive and that selectivity is good
The small-molecule fluorescent probe of line state oxygen is of great significance, and it is big that it can provide biology in singlet oxygen targeting cell system in real time
The important space distributed intelligence of molecule can accurately detect the content of internal singlet oxygen, for the pre- of certain diseases in due course
Anti-, diagnosis and the research of pathology have highly important directive significance [K.Tanaka, T.Miura, N.Umezawa,
Y.Urano,K.Kikuchi,T.Higuchi,T.Nagano,Rational design of fluorescein-based
fluorescence probes,Mechanism-based design of a maximum fluorescence probe
for singlet oxygen,J.Am.Chem.Soc.,2001,123(11),2530.].It is reported at present to be used to detect list
The method of line state oxygen is mainly include the following types: (1) phosphorimetry, detects the standard method of singlet oxygen, utilize singlet oxygen
The near-infrared phosphorescence generated at 1268nm itself is quenched to be detected, for this method to organism without infringement, selectivity is high, but sensitive
Spend that low, detecting signal is weak, is not used to very low concentrations1O2Detection [K.Andersen, Z.Cao, P.R.Ogilby,
L.Poulsen,I.Zebger,J.Phys.Chem.A.2002,106,8488.].(2) Chemical Trapping absorption photometry, using 9,
10- diphenylanthrancene (DPA) with1O2Characteristic reaction generate the variation that stable endoperoxides object causes DPA absorption spectrum, lead to
The variation of detection DPA absorption spectrum is crossed to measure1O2, this method is selectively good, though sensitivity is more much higher than the detection of 1268nm phosphorescence
[M.J.Steinbeck,A.U.Khan,M.J.Karnovsky,Extracellular production of singlet
oxygen by stimulated macrophages quantified using 9,10-diphenylanthracene and
Perylene in a polystyrene film, J.Biol.Chem., 1993,268 (21), 15649.], but this method is to be based on
Absorption spectrum, so sensitivity is still lower.(3) organic fluorescence sonde method is the organic glimmering of detection means using fluorescence signal
Light probe method includes two classes: (a) being utilized1O2It is reacted with the fluoresceins probe molecule specificity with anthracene nucleus, so that probe is by original
The non-fluorescent molecule come becomes fluorescent both molecule, for1O2Detection (N.Umezawa, K.Tanaka, Y.Urano,
K.Kikuchi,T.Higuchi,T.Nagano,Angew.Chem.Int.Ed.Engl.1999,38,2899；K.Tanaka,
T.Miura,N.Umezawa,Y.Urano,K.Kikuchi,T.Higuchi,T.Nagano,J.Am.Chem.Soc.2001,
123,2530.).This method detection time is short, high sensitivity, but is not suitable for low ph environment and real-time detection.(b) it utilizes
Energy transmission between fluorescent probe molecule, excitation probe molecule issue strong delayed fluorescence, and then for detecting1O2
(A.A.Krasnovskii,C.Schweitzer,H.Leismann,C.Tanielian,E.A.Luk’yanets,Quantum
Electron.,2000,30,445；A.A.Krasnovskii,M.E.Bashtanov,N.N.Drozdova,
O.A.Yuzhakova,E.A.Luk'yanets,Quantum Electron.,2002,32,83.).This kind of probe mainly has phthalein
Cyanine dyes and seaweed oxazine derivatives etc. can issue fluorescence for detecting after the energy for receiving singlet oxygen near 700nm.
(4) chemiluminescence probe method, this be it is a kind of based on Photo-induced electron transfer mechanism singlet oxygen fluorescence probe (X.H.Li,
G.X.Zhang, H.M.Ma, D.Q.Zhang, J.Li, D.B.Zhu, J.Am.Chem.Soc.2004,126,11543.), this kind of spy
Needle detects speed fastly and has very high sensitivity and selectivity, but poorly water-soluble well, is unfavorable for biosystem1O2Survey
It is fixed.(5) rare-earth fluorescent probe, long-life phosphors feature of the Yuan Jingli group based on rare-earth fluorescent complex, is prepared for a series of
Rare-earth fluorescent probe has obtained preferable effect (Yuan Jingli, Song using time-resolved fluorescence detection technique measurement singlet oxygen
Wave, Wang Guilan, Tan Mingqian, a kind of singlet oxygen fluorescence probe and its application based on europium complex, Chinese invention patent, application
Numbers 200510130851.9；Yuan Jingli, Song Bo, Wang Guilan, a kind of singlet oxygen europium coordination compound fluorescent probe and its application, China
Patent of invention, application number: 200510045768.1；Yuan Jingli, Song Bo, Wang Guilan, a kind of terbium coordination compound singlet oxygen fluorescence spy
Needle and its application, Chinese invention patent, application number 200510045767.7), the excitation wavelength of this kind of complex is in ultra-violet (UV) band,
Measurement1O2When, biosystem is had damage (B.Song.G.L.Wang.M.Q.Tan.J.L.Yuan.New J.Chem.2005,
29,1431.).Be recently reported rhenium (I) complex singlet oxygen phosphorescence probe (Y.J.Liu, K.Z.Wang,
Eur.J.Inorg.Chem., 2008,5214.), and applied for that series of patents discloses a series of single line of rutheniums or complex of iridium
State oxygen phosphorescence probe (high water-solubility ruthenium metal complex singlet oxygen fluorescent probe and its preparation and application, the patent No.: ZL
2011 1 0204287.6；Application of the ruthenium complex of Hdppz ligand as singlet oxygen fluorescence probe ", the patent No.:
ZL2011101593710；The preparation and its application of ruthenium and iridium metal complex singlet oxygen fluorescent probe, the patent No.: ZL 2008
1 0240591.4.), also have recently other study groups report ruthenium complex singlet oxygen phosphorescence probe (Z.Q.Ye, B.Song,
Y.J.Yin,R.Zhang,J.L.Yuan,Development of singlet oxygen-responsive
phosphorescent ruthenium(II)complexes,Dalton Trans.2013,4214380.).But these probes
Sensitivity still need to improve.
Summary of the invention
The purpose of the present invention is develop excited by visible light, high sensitivity it is novel1O2Fluorescence probe.
Technical scheme is as follows:
A kind of ruthenium binuclear complex containing anthracycline derivatives ligand, structural formula are [Ru (L2)2(H2L1)Ru(L2)2]
Xk, wherein X be counter anion, X be negative monovalent ion when, k=4；X be negative divalent ion when, k=2.L=bpy or phen etc.
Azepine bidentate ligand；Bpy, phen and H2L1Its structural formula is shown below respectively:
Above-mentioned counter anion is mostly the ion of negative one valence, such as Cl-、ClO4 -、PF6 -、NO3 -、CF3SO3 -、BF4 -。
The specific example of complex of the invention is for example:
Complex [Ru (bpy)2(H2L1)Ru(bpy)2]Cl4Structure be shown below:
Above-mentioned complex [Ru (bpy)2(H2L1)Ru(bpy)2]Cl4It can be prepared by the following method:
9,10- anthracene dialdehyde (Ryu, the D. first synthesized by literature method；Park,E.；Kim,D.S.；Yan,S.H.；Lee,
J.Y.；Chang,B.Y.；Ahn,K.H.,J.Am.Chem.Soc.,2008,130,2394；Kim,H.S.；Moon,H.S.；
Jang,D.O.,Superamol.Chem.,2006,18,97；Klanderman,B.H.,J.Org.Chem.,1966,31,
2618.) and 1,10- phenanthroline -5,6- diketone is condensed synthesis critical ligand H in the presence of ammonium acetate/acetic acid2L1；Then H2L1
With Ru (bpy)2Cl22H2After O reacts in ethylene glycol, through Al2O3Column chromatography purification.
It is of the invention using transition metal ruthenium or iridium as center ion, be that the complex of ligand has single line using anthracycline derivatives
The performance of state oxygen fluorescence probe, suitable for neutral and alkaline system1O2It is qualitative and/or quantitative determination.
The application process of the singlet oxygen fluorescence probe of the complex are as follows: in neutral or alkaline solution, using described
Complex is as in fluorescence probe capture system1O2And the endoperoxides object of the complex, body are generated with singlet oxygen effect
The fluorescence intensity of system significantly increases, and can detecte in system by the fluorimetry of excited by visible light1O2.It comprises the concrete steps that:
1. complex of the invention is added in the known neutrality or alkaline system that effectively can generate singlet oxygen,
Under a series of singlet oxygen concentration conditions, the fluorescence intensity and absorbance of system are measured by excited by visible light, are obtained opposite
The fluorescence quantum efficiency answered obtains standard curve of the fluorescence quantum efficiency relative to singlet oxygen concentration；
2. containing the complex neutrality or alkaline buffer solution in a certain amount of solution to be measured is added, pass through visible light
The fluorescence intensity and absorbance for exciting measurement system, are calculated its fluorescence quantum efficiency；
3. the logarithm of the fluorescence intensity measured using step 2 does abscissa as ordinate, with the log concentration of singlet oxygen
Mapping, linear segment are the standard curve for measuring singlet oxygen concentration.
Singlet oxygen phosphorescence probe excited by visible light disclosed by the invention, and peroxide in it is generated after reacting with singlet oxygen
Compound fluorescence intensity enhances the big singlet oxygen fluorescence probe of amplitude.Probe of the invention has the advantages that
1. suitable for neutral and alkaline system1O2Measurement.
2. singlet oxygen detection sensitivity with higher, lowest detection 3.12-2.7nM.
3. having preferable selectivity, other active oxygen species (H2O2, OH, ONOO-) system fluorescence signal is caused to enhance
Amplitude very little.
Detailed description of the invention
Fig. 1 is illustrated neutral with singlet oxygen in alkaline system to complex [Ru (bpy)2(H2L1)Ru(bpy)2]Cl4
The influence of (5 μM) absorption spectrum, in which: (a) is the change of the absorption spectrum in the 50mM phosphate buffer solution of pH=7.0
Change；(b) be absorption spectrum in the 0.1M carbonate buffer solution of pH=9.95 variation.The illustration of Fig. 1 (a) and (b) point
Complex [the Ru (bpy) in neutral and alkaline system is not illustrated2(H2L1)Ru(bpy)2]Cl4The fluorescence intensity of (5 μM) with
Relationship in system between singlet oxygen concentration.
Fig. 2 is illustrated neutral with singlet oxygen in alkaline system to complex [Ru (bpy)2(H2L1)Ru(bpy)2]Cl4
The influence of (5 μM) luminescent spectrum, in which: (a) is the change of the fluorescence spectrum in the 50mM phosphate buffer solution of pH=7.0
Change；(b) be fluorescence spectrum in the 0.1M carbonate buffer solution of pH=9.95 variation.The illustration of Fig. 2 (a) and (b) point
Complex [the Ru (bpy) in neutral and alkaline system is not illustrated2(H2L1)Ru(bpy)2]Cl4The fluorescence intensity of (5 μM) with
Relationship in system between singlet oxygen concentration.
Fig. 3 illustrates the complex [Ru (bpy) in neutral and alkaline system2(H2L1)Ru(bpy)2]Cl4(5 μM) it is glimmering
Relationship between photo-quantum efficiency and singlet oxygen concentration, in which: (a) is in the 50mM phosphate buffer solution of pH=7.0；
It (b) is in the 0.1M carbonate buffer solution of pH=9.95.
Fig. 4 illustrates complex [Ru (bpy) in neutral and alkaline system2(H2L1)Ru(bpy)2]Cl4It is (1.67 μM) and living
The effect of property oxygen species ([ROS]=0.53 μM), in which: (a) is in the 50mM phosphate buffer solution of pH=7.0；(b) it is
In the 0.1M carbonate buffer solution of pH=9.95.
Specific embodiment
Below by embodiment, the present invention is further described.
Embodiment one, ligand H2L1Synthesis:
78mg (0.33mmol) 9,10- anthracene dialdehyde and 140mg (0.66mmol) 1,10- o-phenanthroline -5,6- diketone and
500mg (0.33mmol) ammonium acetate is dissolved in 20ml acetic acid, N2The lower 6h that flows back of protection.Solution is added in ice water after reaction, is put
A night is set, a large amount of yellow mercury oxides occurs.It filters, it is dry.Methanol is washed, dry.Gained crude product solubility is excessively poor, is not easy to mention
It is pure.
Embodiment two, [Ru (bpy)2(H2L1)Ru(bpy)2]Cl4Synthesis:
H2L1(0.0307g,0.05mmol)、Ru(bpy)2Cl2·2H2O (0.0520g, 0.1mmol) is in 10ml ethylene glycol
In, lower 140 DEG C of nitrogen protection are stirred to react 12 hours, and reaction solution becomes peony by initial purple, cooling.By ethylene glycol
It screws out, product solid CH2Cl2/CH3OH (volume ratio 20/1) dissolution, with neutral Al2O3(200-300 mesh) column chromatography for separation, is washed
Proposing agent is 20~50/1CH of volume ratio2Cl2/CH3OH, collects main red zone, and revolving removes solvent.By obtained solid second
Nitrile/ether diffusion recrystallization, obtains red solid 0.045g, yield 56.9%.Matrix Assisted Laser Desorption ionizes flight time matter
Spectrum: m/z=360.9 ([M-4Cl?]+), M=C80H54N16Cl4Ru2, calculated value: 360.0 ([M-4Cl?]+).Proton magnetic is total
Vibration spectrum (δH, ppm, 400MHz, DMSO-d6): 9.20 (d, J=7.36Hz, 2H), 9.03 (d, J=6.88Hz, 2H), 8.91 (d,
J1=8.34Hz, J2=11.98Hz, 8H), 8.25 (t, J=7.96Hz, 4H), 8.16 (m, 8H), 7.97 (s, 8H), 7.91 (d, J
=5.40Hz, 4H), 7.72 (d, J=5.48Hz, 4H), 7.64 (m, 8H), 7.43 (s, 4H).Infrared spectroscopy (KBr, cm-1):
3422br, 1596w, 1461w, 1443w, 1384s, 1353s, 767m, 726w.Elemental analysis [C80H54N16Cl4Ru2·
4CH3CN·18.5H2O (F.W.=2079.46)] calculated value: C, 50.79；H, 4.99；N, 13.46%；Measured value: C, 50.39；
H, 4.23；N, 14.05%.
Three singlet oxygen of embodiment senses property and measurement
With [Ru (bpy)2(H2L1)Ru(bpy)2]Cl4For, introduce complex of the present invention as fluorescence probe neutrality with
The method and detection performance of singlet oxygen are detected in alkaline solution.
In neutral system1O2Measurement: first in the phosphate buffer solution of the pH=7.0 containing 10mM NaOCl plus
Enter complex, H then is added in the system2O2, H2O2/ NaOCl system singlet oxygen yield in neutral solution is almost
100% (A.M.Held, D.J.Halko, J.K.Hurst, J.Am.Chem.Soc.1978,100,5732-5740.).With H2O2
Addition, constantly generate in system1O2, generated1O2Acted on complex, the anthracene nucleus in complex 350nm-400nm it
Between absorption constantly reduce, it was demonstrated that anthracene nucleus be with1O2The active group of reaction, while system fluorescence intensity gradually increases.
In alkaline system1O2Measurement: contain 10mM Na2MoO4PH=9-11 carbonate buffer solution in be added
Then H is added in complex in system2O2, H2O2/Na2MoO4System can effectively generate singlet oxygen in alkaline solution
(K.Tanaka,T.Miura,N.Umezawa,Y.Urano,K.Kikuchi,T.Higuchi,T.Nagano,
J.Am.Chem.Soc.,2001,123,2530-2536；M.Q.Tan,B.Song,G.L.Wang,J.L.Yuan,Free
Radic.Biol.Med.,2006,40,1644–1653.).With H2O2Addition, system constantly generates1O2, generated1O2
Acted on complex, absorption of the anthracene nucleus in complex between 350nm-400nm constantly reduces, it was demonstrated that anthracene nucleus be with1O2Reaction
Active group, while system fluorescence intensity gradually increases.
Complex has preferable detection performance to singlet oxygen in neutral and alkaline solution, referring to FIG. 1 to FIG. 2, in
Singlet oxygen under the conditions of property is by H2O2/ NaClO system is generated in the 50mM phosphate buffer solution of pH=7.0；Alkaline ring
Singlet oxygen can be by H in border2O2/Na2MoO4Carbonate buffer solution of the system in the 0.1M of pH=9.95 generates.Instrument is used in measurement
Device is GBC Cintra 10e ultraviolet-visible spectrophotometer and Cary Eclipse sepectrophotofluorometer.In neutral (alkali
Property) H is added in buffer solution2O2System can generate1O2, with1O2With the effect of complex, anthracene nucleus part is in 350nm-
Absorption between 400nm constantly reduces, as shown in Figure 1, it was demonstrated that anthracene nucleus be with1O2The active group of reaction.H be not added2O2When
System almost without fluorescent emission, with1O2The increase of concentration ties up to the fluorescent emission at 610nm in 464nm light excitation lower body
It gradually increases, (arrow direction is in Fig. 2 as shown in Figure 21O2The increased direction of concentration), have in neutral and alkalinity solution
Singlet oxygen and without fluorescence intensity ratio in the presence of singlet oxygen respectively up to 5.4 and 7.6, quantum efficiency increase respectively reaches 7.6 Hes
8.8.The fluorescence enhancement of system be due to complex with1O2Effect generates its endoperoxides object to influence the emissivity of fluorophor
Matter changes its luminescent properties to issue stronger fluorescence.The fluorescent emission at 610nm of system under the excitation of 464nm light
Intensity with1O2Relationship between concentration as shown in figure 3, the neutral logarithm with the luminous intensity in alkaline buffer to singlet
Oxygen concentration logarithm mapping results are shown in illustration, and the linear segment simulated in illustration obtains equation: lgI=3.56+ respectively
0.328lg[1O2] (n=15, r=0.986) and lgI=3.82+0.403lg [1O2] (n=15, r=0.993).By illustration
In straight line portion as standard curve, any unknown system can be measured in neutral and alkaline conditions using complex as probe
In singlet oxygen concentration.
In the effect experiment of complex and active oxygen species, complex and H2O2, OH, ONOO-The effect of isoreactivity oxygen species
When system fluorescence intensity change very little, and complex with1O2The fluorescence of system greatly enhances after effect, as shown in figure 4, this shows
Complex pair1O2With good selectivity.It is right in neutral and alkaline conditions1O2Detection minimum concentration according to background standard
It is respectively 7.6nM and 5.2nM that the three times of deviation, which calculate, shows the complex pair1O2With very high sensitivity.
Claims (1)
1. a kind of binuclear ruthenium is used to prepare singlet oxygen phosphorescence probe, the binuclear ruthenium by cation and yin from
Sub- Cl-Composition, which is characterized in that the cation is [(bpy)2Ru(H2L1)Ru(bpy)2]4+, structural formula is as shown below:
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| 钌(II)多吡啶配合物与DNA相互作用的光切割与荧光性质研究;王海滔等，;《化学学报》;20101231;第1507-1512页 |
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