CN106749421A - The preparation and its application of highly sensitive singlet oxygen phosphorescence probe - Google Patents
The preparation and its application of highly sensitive singlet oxygen phosphorescence probe Download PDFInfo
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- CN106749421A CN106749421A CN201611039001.2A CN201611039001A CN106749421A CN 106749421 A CN106749421 A CN 106749421A CN 201611039001 A CN201611039001 A CN 201611039001A CN 106749421 A CN106749421 A CN 106749421A
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000523 sample Substances 0.000 title description 27
- 230000007935 neutral effect Effects 0.000 claims abstract description 22
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 9
- 239000012736 aqueous medium Substances 0.000 claims abstract 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims 2
- 150000001768 cations Chemical class 0.000 claims 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 15
- 230000035945 sensitivity Effects 0.000 abstract description 10
- 238000001514 detection method Methods 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 230000008859 change Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000007853 buffer solution Substances 0.000 description 7
- 239000007850 fluorescent dye Substances 0.000 description 7
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- 238000000862 absorption spectrum Methods 0.000 description 6
- 150000001454 anthracenes Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 206010028980 Neoplasm Diseases 0.000 description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 3
- 229940045799 anthracyclines and related substance Drugs 0.000 description 3
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- 229910052741 iridium Inorganic materials 0.000 description 3
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- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 239000011684 sodium molybdate Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910019093 NaOCl Inorganic materials 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000012327 Ruthenium complex Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
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- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- 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
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-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
- 241001474374 Blennius Species 0.000 description 1
- 208000002177 Cataract Diseases 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 102000007330 LDL Lipoproteins Human genes 0.000 description 1
- 108010007622 LDL Lipoproteins Proteins 0.000 description 1
- 208000002720 Malnutrition Diseases 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 206010037423 Pulmonary oedema Diseases 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- OJNBAGCXFHUOIQ-UHFFFAOYSA-N [Re+] Chemical compound [Re+] OJNBAGCXFHUOIQ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 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
- SBRUFOSORMQHES-UHFFFAOYSA-N anthracene-9,10-dialdehyde Chemical compound C1=CC=C2C(C=O)=C(C=CC=C3)C3=C(C=O)C2=C1 SBRUFOSORMQHES-UHFFFAOYSA-N 0.000 description 1
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
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- 230000036755 cellular response Effects 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
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- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 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
- 206010020718 hyperplasia Diseases 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003859 lipid peroxidation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000002540 macrophage Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 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
- 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
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 208000020016 psychiatric disease Diseases 0.000 description 1
- 208000005333 pulmonary edema Diseases 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 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
- 230000011664 signaling Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses binuclear ruthenium preparation method and its singlet oxygen sensor in terms of application.As abscissa, the logarithm value of luminous intensity draws out standard working curve to logarithm value with the concentration of singlet oxygen for ordinate, for determining singlet oxygen concentration in neutral and alkaline aqueous medium.The method has excited by visible light, high sensitivity, high selectivity and easy-operating advantage.
Description
Technical field
The present invention relates to singlet oxygen in solution (1O2) measure, a specifically class contains anthracycline derivatives part
A kind of preparation and its application of double-core ruthenium metal complex singlet oxygen phosphorescence probe.
Background technology
Singlet oxygen is a kind of unstable existence form that oxygen molecule is in high energy excitation state, and singlet oxygen is used as organic
A kind of precious reagent in chemistry, in many photochemistry and optical-biological reaction, such as light degradation, the light conversion of pollutant, chemiluminescence,
During organism deterioration by oxidation, even photocarcinogenesis etc., highly important role is all play.In organic synthesis,
Singlet oxygen causes that oxygen is introduced in the single-minded organic compound of High level of stereoselectivity becomes extremely easy.In living things system, single line
State oxygen has great influence to life system, and the physiology oxidation of singlet is more and more interested to researchers.It is single
Line state oxygen plays an important role in cellular damage and apoptosis, and it is likely to result in damages to the strong oxidizing property of body, so as to draw
The generation of body lipid peroxidation is played, causes 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, trigger the disease relevant 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 and control such as hyperplasia, differentiation, apoptosis of cell
Play 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.].Conversely, people can also utilize the strong oxidizing property of singlet oxygen
Matter goes to kill malignant cell or tissue, reaches the purpose for curing cancer.Experiment finds, when malignant cell obtains and ties
The ability of singlet oxygen sensitizers medicine is closed when being noticeably greater than normal structure, by after illumination, the singlet that drug molecule is produced
Oxygen just can optionally kill tumour cell.The singlet oxygen for medically being produced with the photosensitive method of methylene blue come to Plasma disinfection and
The photodynamic diagnosis of tumour, this photodynamic therapy technology tumour diagnosis and treatment in have a wide range of applications before
Scape.Singlet oxygen is closely related with human health and disease, is the focus of current life science and chemical science crossing research.
Because singlet oxygen has such consequence during photochemistry and photo-biological,1O2Detection receives much attention,
Particularly in living things system1O2Detection increasingly cause the concern of researcher.Research and development high sensitivity and the good list of selectivity
The small-molecule fluorescent probe of line state oxygen is significant, and it can be given biological big in singlet oxygen targeting cell system in real time
The important space distributed intelligence of molecule, can exactly detect the content of internal singlet oxygen in good time, pre- for some diseases
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.].At present reported for detecting list
The method of line state oxygen mainly has following several：(1) phosphorimetry, detects the standard method of singlet oxygen, using singlet oxygen
The near-infrared phosphorescence produced at 1268nm itself is quenched to be detected, this method is to organism without infringement, and selectivity is high but sensitive
The low, detecting signal of degree is weak, be 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- diphenylanthrancenes (DPA) with1O2The endoperoxide of characteristic reaction generation stabilization cause the change of DPA absorption spectrums, lead to
The change of detection DPA absorption spectrums is crossed to measure1O2, this method is selectively good, though sensitivity detects much higher than 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 relatively low.(3) organic fluorescence sonde method, is the organic glimmering of detection means using fluorescence signal
Light probe method includes two classes：A () utilizes1O2Reacted with the fluoresceins probe molecule selectivity with anthracene nucleus so that probe is by original
The non-fluorescent molecule for coming is changed into fluorescent both molecule, so as to be used 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.).The method detection time is short, and sensitivity is high, but is not suitable for low ph environment and real-time detection.B () utilizes
Energy transmission between fluorescent probe molecule, excites probe molecule to send 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., are used to detect when that can send fluorescence after the energy for receiving singlet oxygen near 700nm.
(4) chemiluminescence probe method, this be a class be 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
Pin detection speed is fast and with sensitivity very high and selective well, but poorly water-soluble, is unfavorable for living things system1O2Survey
It is fixed.(5) rare-earth fluorescent probe, Yuan Jing profits group is based on the long-life phosphors feature of rare-earth fluorescent complex, is prepared for a series of
Rare-earth fluorescent probe, determines singlet oxygen and has obtained preferable effect (Yuan Jingli, Song using time-resolved fluorescence detection technique
Ripple, 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, a kind of Wang Guilan, terbium coordination compound singlet oxygen fluorescence are visited
Pin and its application, Chinese invention patent, application number 200510045767.7), the excitation wavelength of this kind of complex is in ultra-violet (UV) band,
Determine1O2When, living things system is damaged wound (B.Song.G.L.Wang.M.Q.Tan.J.L.Yuan.New J.Chem.2005,
29,1431.).Be recently reported a singlet oxygen phosphorescence probe for rhenium (I) complex (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；The ruthenium complex of Hdppz parts as singlet oxygen fluorescence probe application ", 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 seminar 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.
The content of the invention
The purpose of the present invention is exploitation excited by visible light, high new of sensitivity1O2Fluorescence probe.
Technical scheme is as follows：
A kind of ruthenium binuclear complex containing anthracycline derivatives part, its structural formula is [Ru (L2)2(H2L1)Ru(L2)2]
Xk, wherein X is counter anion, when X is negative monovalent ion, k=4；When X is negative divalent ion, 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 generally the ion of negative one valency, 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]Cl4Can be prepared by the following method：
9,10- anthracene dialdehyde (Ryu, the D. for first being 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.) it is condensed in the presence of ammonium acetate/acetic acid and synthesizes critical ligand H with 1,10- phenanthroline -5,6- diketone2L1；Then H2L1
With Ru (bpy)2Cl22H2After O reacts in ethylene glycol, through Al2O3Chromatography over CC.
The ion centered on transition metal ruthenium or iridium of the invention, the complex with anthracycline derivatives as part has single line
The performance of state oxygen fluorescence probe, it is adaptable in neutral and alkaline system1O2It is qualitative and/or quantitative determination.
The application process of the singlet oxygen fluorescence probe of the complex is：In neutral or alkaline solution, using described
Complex is used as in fluorescence probe capture system1O2And the endoperoxide for generating the complex, body are acted on singlet oxygen
The fluorescence intensity of system is significantly increased, can be with detection architecture by the fluorimetry of excited by visible light1O2.Comprise the concrete steps that：
1. complex of the invention is added in the known neutrality or alkaline system that can effectively produce singlet oxygen,
Under a series of singlet oxygen concentration conditions, the fluorescence intensity and absorbance of system are determined by excited by visible light, obtain relative
The fluorescence quantum efficiency answered, obtains standard curve of the fluorescence quantum efficiency relative to singlet oxygen concentration；
2. a certain amount of solution to be measured is added in the neutrality or alkaline buffer solution containing the complex, by visible ray
The fluorescence intensity and absorbance of measure system are excited, its fluorescence quantum efficiency is calculated；
3. the logarithm value of the fluorescence intensity for being measured with step 2 is ordinate, and abscissa is done with the log concentration of singlet oxygen
Mapping, linear segment is the standard curve for determining singlet oxygen concentration.
Singlet oxygen phosphorescence probe excited by visible light disclosed by the invention, and with singlet oxygen reaction after generate its interior peroxide
The big singlet oxygen fluorescence probe of compound fluorescence intensity enhancing amplitude.Probe of the invention has the following advantages that：
1. suitable for neutral and alkaline system1O2Measure.
2. there is singlet oxygen detection sensitivity higher, lowest detection is 3.12-2.7nM.
3. there is preferably selectivity, other active oxygen species (H2O2, OH, ONOO-) cause the enhancing of system fluorescence signal
Amplitude very little.
Brief description of the drawings
Fig. 1 illustrates in neutral and alkaline system singlet oxygen to complex [Ru (bpy)2(H2L1)Ru(bpy)2]Cl4
The influence of (5 μM) absorption spectrum, wherein：A () is the change of the absorption spectrum in the 50mM PBSs of pH=7.0
Change；B () is the change of the absorption spectrum in the 0.1M carbonate buffer solutions of pH=9.95.The illustration point of Fig. 1 (a) and (b)
Complex [the Ru (bpy) in neutral and alkaline system is not illustrated2(H2L1)Ru(bpy)2]Cl4The fluorescence intensity of (5 μM) with
Relation in system between singlet oxygen concentration.
Fig. 2 illustrates in neutral and alkaline system singlet oxygen to complex [Ru (bpy)2(H2L1)Ru(bpy)2]Cl4
The influence of (5 μM) luminescent spectrum, wherein：A () is the change of the fluorescence spectrum in the 50mM PBSs of pH=7.0
Change；B () is the change of the fluorescence spectrum in the 0.1M carbonate buffer solutions of pH=9.95.The illustration point of Fig. 2 (a) and (b)
Complex [the Ru (bpy) in neutral and alkaline system is not illustrated2(H2L1)Ru(bpy)2]Cl4The fluorescence intensity of (5 μM) with
Relation 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
Relation between photo-quantum efficiency and singlet oxygen concentration, wherein：A () is in the 50mM PBSs of pH=7.0；
B () is in the 0.1M carbonate buffer solutions 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), wherein：A () is in the 50mM PBSs of pH=7.0；B () is
In the 0.1M carbonate buffer solutions of pH=9.95.
Specific embodiment
Below by embodiment, the present invention is further described.
Embodiment one, part H2L1Synthesis：
78mg (0.33mmol) 9,10- anthracenes 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 backflow 6h of protection.By in solution addition frozen water after reaction, put
Put a night, a large amount of yellow mercury oxides occur.Suction filtration, dries.Methyl alcohol is washed, and is dried.Gained crude product solubility is excessively poor, is difficult to carry
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, nitrogen protects lower 140 DEG C of stirring reactions 12 hours, and reaction solution becomes laking, cooling by initial purple.By ethylene glycol
Screw out, product solid CH2Cl2/CH3OH (volume ratio 20/1) dissolves, and uses neutral Al2O3(200-300 mesh) column chromatography for separation, washes
Agent is proposed for 20~50/1CH of volume ratio2Cl2/CH3OH, collects main red zone, and revolving removes solvent.By gained 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 to
Spectrum of shaking (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 spectrum (KBr, cm-1)：
3422br, 1596w, 1461w, 1443w, 1384s, 1353s, 767m, 726w.Elementary 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%.
The singlet oxygen of embodiment three senses property and measure
With [Ru (bpy)2(H2L1)Ru(bpy)2]Cl4As a example by, introduce complex of the present invention as fluorescence probe it is neutral with
The method and detection performance of singlet oxygen are detected in alkaline solution.
In neutral system1O2Measure：Add first in the PBS of the pH=7.0 containing 10mM NaOCl
Enter complex, then add H in the system2O2, H2O2/ NaOCl systems 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 produced in system1O2, it is produced1O2With complex effect, 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 strengthens.
In alkaline system1O2Measure：Containing 10mM Na2MoO4PH=9-11 carbonate buffer solution in add
Complex, then adds H in system2O2, H2O2/Na2MoO4System can effectively produce 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 produces1O2, it is produced1O2
With complex effect, the absorption of anthracene nucleus in complex between 350nm-400nm constantly reduces, it was demonstrated that anthracene nucleus be with1O2Reaction
Active group, while system fluorescence intensity gradually strengthens.
Complex has preferably detection performance in neutral and alkaline solution to singlet oxygen, referring to Fig. 1~Fig. 2, in
Singlet oxygen under the conditions of property is by H2O2/ NaClO systems are produced in the 50mM PBSs of pH=7.0；Alkaline ring
Singlet oxygen can be by H in border2O2/Na2MoO4System is produced in the carbonate buffer solution of the 0.1M of pH=9.95.Measure instrument
Device is GBC Cintra 10e ultraviolet-visible spectrophotometers and Cary Eclipse sepectrophotofluorometers.In neutral (alkali
Property) H is added in cushioning liquid2O2System can be produced1O2, with1O2With the effect of complex, anthracene nucleus part is in 350nm-
Absorption between 400nm is constantly reduced, as shown in Figure 1, it was demonstrated that anthracene nucleus be with1O2The active group of reaction.H is not being added2O2When
System does not almost have fluorescent emission, with1O2The increase of concentration, excites lower body to tie up to the fluorescent emission at 610nm in 464nm light
Gradually strengthen, (arrow direction is in Fig. 2 as shown in Figure 21O2The increased direction of concentration), have in neutral and alkalescence 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 Increasing of system be due to complex with1O2Effect generates its endoperoxide so as to influence the emissivity of fluorophor
Matter, changes its luminescent properties so as to send stronger fluorescence.The fluorescent emission at 610nm of lower system is excited in 464nm light
Intensity with1O2Relation between concentration is as shown in figure 3, the logarithm value of the luminous intensity in neutral and alkaline buffer is to singlet
Oxygen concentration logarithm value mapping results are shown in illustration, and the linear segment in simulation illustration obtains equation respectively：LgI=3.56+
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 in neutral and alkaline conditions determined with complex as probe
In singlet oxygen concentration.
In the effect experiment of complex and active oxygen species, complex and H2O2, OH, ONOO-Isoreactivity oxygen species are acted on
When system fluorescence intensity change very little, and complex with1O2The fluorescence of system is greatly enhanced after effect, as shown in figure 4, this shows
Complex pair1O2With good selectivity.It is right in neutral and alkaline conditions1O2Detection least concentration according to background standard
The three times of deviation are calculated and are respectively 7.6nM and 5.2nM, show the complex pair1O2With sensitivity very high.
Claims (5)
1. the binuclear ruthenium in the present invention, is made up of cation and anion, it is characterised in that the cation is
[(bpy)2Ru(H2L1)Ru(bpy)2]4+, structural formula is as shown below：
2. binuclear ruthenium according to claim 1, it is characterised in that the anion is inorganic salt anionic.
3. binuclear ruthenium according to claim 2, it is characterised in that the inorganic salt anionic is Cl-。
4. the preparation method of binuclear ruthenium according to claim 3, it is characterised in that preparation process is simple to operation：
By H2L1With Ru (bpy)2Cl2After back flow reaction in ethylene glycol, neutral Al is used2O3(200-300 mesh) column chromatography for separation, washes
Agent is proposed for 20~50/1CH of volume ratio2Cl2/CH3OH, collects main red zone, and revolving removes solvent.By gained solid second
Nitrile/ether diffusion recrystallization, obtains target product.
5. binuclear ruthenium according to claim 3, it is characterised in that can be vertical seat according to the logarithm value of luminous intensity
During mark, the logarithm value of singlet oxygen concentration are tried to achieve and wait to ask neutral and alkaline aqueous medium for standard working curve that abscissa is drawn
Singlet oxygen concentration.
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| CN109251746A (en) * | 2018-11-23 | 2019-01-22 | 曲靖师范学院 | The preparation and its application of anthracene nucleus bridged binuclear ruthenium complex fluorescence probe |
| CN109796503A (en) * | 2018-10-26 | 2019-05-24 | 云南大学 | A kind of preparation method of double-core cyclopentadienyl type ruthenium complex and its application in antitumor |
| CN110511249A (en) * | 2019-08-26 | 2019-11-29 | 北京师范大学 | The preparation and application of near-infrared luminous ruthenium complex |
| CN108727277B (en) * | 2018-05-24 | 2021-03-30 | 陕西师范大学 | Singlet oxygen highly selective aggregation-induced chemiluminescence probe and preparation method and application thereof |
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| 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 |
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| CN108727277B (en) * | 2018-05-24 | 2021-03-30 | 陕西师范大学 | Singlet oxygen highly selective aggregation-induced chemiluminescence probe and preparation method and application thereof |
| CN109796503A (en) * | 2018-10-26 | 2019-05-24 | 云南大学 | A kind of preparation method of double-core cyclopentadienyl type ruthenium complex and its application in antitumor |
| CN109796503B (en) * | 2018-10-26 | 2021-04-20 | 云南大学 | Preparation method of dinuclear metallocene ruthenium complex and application of dinuclear metallocene ruthenium complex in tumor resistance |
| CN109251746A (en) * | 2018-11-23 | 2019-01-22 | 曲靖师范学院 | The preparation and its application of anthracene nucleus bridged binuclear ruthenium complex fluorescence probe |
| CN109251746B (en) * | 2018-11-23 | 2021-10-08 | 曲靖师范学院 | Preparation and application of anthracene ring bridged binuclear ruthenium complex fluorescent probe |
| CN110511249A (en) * | 2019-08-26 | 2019-11-29 | 北京师范大学 | The preparation and application of near-infrared luminous ruthenium complex |
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