CN1811430A - Singlet oxygen europium coordination compound fluorescent probe and application thereof - Google Patents
Singlet oxygen europium coordination compound fluorescent probe and application thereof Download PDFInfo
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Abstract
The present invention relates to a new-type singlet oxygen europium fluorescent probe and its application. It is a coordination compound formed by using trivalent europium ion Eu3+ and 2, 2':6'2''-ditripyridine skeleton structure ligand containing functional group. Said invention also provides the structure formula of the described ligand. Said coordination compound can be used for making fluorescent determination of singlet oxygen.
Description
Technical field
The present invention relates to singlet oxygen in the solution (
1O
2) determination techniques, specifically a kind of novel
1O
2The europium coordination compound fluorescent probe novel singlet oxygen fluorescence probe of europium complex (promptly based on) and using.
Background technology
Singlet oxygen (
1O
2) be a kind of excited state of oxygen molecule, it not only is a kind of very useful oxygenant in organic synthesis, but also has crucial physiologically active.In organic synthesis,
1O
2Make that introducing oxygen in highly three-dimensional single-minded organic compound becomes very easy.
1O
2Following several important reaction is arranged: at first,
1O
2Can react with mono-olefin, generate dioxane alkane or hydrocarbon superoxide.The former at room temperature is decomposed into corresponding carbonyls and luminous usually, and the latter then generates beta-unsaturated ketone, allyl alcohol or hydroxyl compound under corresponding condition.Secondly,
1O
2Can with have N, O or S etc. and give electronics heteroatomic activated double bonds reaction, generate 1 of quaternary, and then 2-dioxy ring splits into the compound of twain-aldehyde compound structure.Simultaneously,
1O
2Can the addition reaction of Diels-Alder type take place with chain, ring-type, fragrance, heteroaromatic type conjugated, generate inner oxide.In addition,
1O
2Also can complicated chemistry and physical action take place with carotenoid, amine, phenols and heterocycle compound, make
1O
2In living things system, has very high reactivity.In the life system,
1O
2Be a kind of common active oxygen in the biosome, its character is active, electrophilicity is strong, can react with various biomolecules such as DNA, protein and lipid materials, plays very important physiological action.
1O
2Almost producing as reacting precursor in all biological photooxidation system, is the main working substance of biological cell photoactivate damage.It can destroy erythrocytic cell membrane in the blood, makes cell generation haemolysis; Simultaneously can also with the amino acid effect, suppress the activity of hydroxyl dehydrogenasa and insulin.In immune system,
1O
2Be leukocytes phagocytic, the organic main germifuge of dissolving invasion.
Because
1O
2Have so important effect, detect
1O
2, particularly in the living things system
1O
2More and more cause people's attention.Begin till now the seventies from eighties of last century,
1O
2Detection mainly contain following several method: (1) utilizes
1O
2Self cancellation
1Δ
g→
3∑
gThe phosphorescence of-generation detects
1O
2(document 1:A.A., Jr.Krasnovsky, Biofzika, 1976,21,748).This method selectivity is very high, but sensitivity is low, a little less than the detecting signal, can't be used for low concentration
1O
2Detection.At present, along with the raising of detecting instrument performance, this method has been used in some living things system
1O
2Research (document 2:C.Kiryu, M.Makiuchi, J.Miyazaki, T.Fujinaga, K.Kakinuma, FEBS Lett.1999,443,154 of generation, physiological action and space distribution; Document 3:S.Oelckers, T.Ziegler, I.Michler, B.R der, J.Photochem.Photobiol.B:Biol.1999,53,121; Document 4:L.K.Andersen, P.R.Ogilby, Photochem.Photobiol.2001,73,489; Document 5:L.K.Andersen, Z.Gao, P.R.Ogilby, L.Poulsen, I.Zebger, J.Phys.Chem.A 2002,106, and 8488).(2) utilize
1O
2Fluoresceins probe molecule selectivity reaction with having anthracene nucleus makes probe become the hyperfluorescence molecule by original non-fluorescent molecule, thereby is used for
1O
2Detection (document 6:N.Umezawa, K.Tanaka, Y.Urano, K.Kikuchi, T.Higuchi, T.Nagano, Angew.Chem.Int.Ed.Engl.1999,38,2899; Document 7:K.Tanaka, T.Miura, N.Umezawa, Y.Urano, K.Kikuchi, T.Higuchi, T.Nagano, J.Am.Chem.Soc.2001,123,2530).This method is short, highly sensitive detection time, but is not suitable for low ph environment and detection in real time.(3) utilize 9,10-diphenylanthrancene (DPA) with
1O
2Characteristic reaction generate stable inner oxide, measure by the change of measuring the DPA absorption spectrum
1O
2(document 8:M.J.Stenbeck, A.U.Khan, M.J.Kamovsy, J.Biol.Chem.1992,267,13425; Document 9:M.J.Stenbeck, A.U.Khan, M.J.Kamovsy, J.Biol.Chem.1993,268,15649).This method has been used to measure and has produced in the phagocyte
1O
2, but owing to detect based on absorption spectrum, so sensitivity is lower.(4) utilize
1O
2And the NE BY ENERGY TRANSFER between the probe molecule excites probe molecule to send strong delayed fluorescence, and then is used for
1O
2Detection (document 10:A.A.Jr.Krasnovsky, C.Schweitzer, H.Lesmann, C.Tanielian, E.A.Luk ' yanets, Quantum Electron.2000,30,445; Document 11:A.A.Jr.Krasnovsky, M.E.Bashtanov, N.N.Drozdova, O.A.Yuzhakova, E.A.Luk ' yanets, Quantum Electron.2002,32,83).This method is applicable to multiple system, and the luminescent quantum productive rate is
1O
2The 3-5 of phosphorescence doubly.But detect the sensitization simultaneously of used probe
1O
2Generation, make measurement result produce deviation.(5) a kind of chemoluminescence method based on the photoinduction electronic transfer process detects
1O
2(document 12: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 method selectivity is good, highly sensitive, detection is rapid, but the probe poorly water-soluble is unfavorable in the living things system
1O
2Mensuration.
In recent years, be that the time-resolved fluorometry of probe has been widely used in the multiple mensuration such as immunoassay, DNA hybridization analysis, the analysis of fluorescence microscopy bio-imaging with the rare-earth fluorescent complex.The rare-earth fluorescent complex has characteristics such as fluorescence lifetime is long, the Stokes displacement is big, the fluorescence radiation peak is sharp-pointed, can effectively remove various light at random and sample background fluorescence to fluorimetric influence by differentiating fluorometry service time, measure sensitivity thereby greatly improve.
Summary of the invention
The objective of the invention is time-resolved fluorometry is applied to
1O
2Detection, a kind of highly sensitive, selectivity and good water solubility, applied widely novel are provided
1O
2Europium coordination compound fluorescent probe.
For achieving the above object, the technical solution used in the present invention is:
With rare earth ion with contain anthracene nucleus and replace 2,2 ': 6 ', 2 "-fluorescence probe that the ligand of ter cycloheptapyridine skeleton structure forms, its described ligand structure formula is:
Wherein R is hydrogen (H), alkyl (CnH
2n+1) or phenyl (C
6H
5); Wherein best n=1～6.
Fluorescence probe of the present invention can be used under the multiple environment
1O
2Mensuration, in all kinds of biologies and abiotic environment, promptly utilize probe to catch to produce in the system
1O
2, make the fluorescence intensity of probe change greatly, then by measure probe with
1O
2The variable quantity of fluorescence intensity is measured before and after the effect
1O
2Concentration (produce and growing amount).
Wherein said fluorometry also comprises time-resolved fluorometry and time resolution fluorescent microscope determination method except the fluorometry of routine.
Europium coordination compound fluorescent probe of the present invention can be prepared into singlet oxygen europium coordination compound fluorescent probe
1O
2Detectable and kit.
Fluorescence probe of the present invention has following advantage:
1. of the present invention novel
1O
2Fluorescence probe has well water-soluble, is applicable in the living things system
1O
2Mensuration.
2. of the present invention novel
1O
2Fluorescence probe stability is high, can long preservation use, and is applicable to multiple environment such as faintly acid, neutrality and alkalescence.
3. of the present invention novel
1O
2Fluorescence probe has high sensitivity, and its lowest detectable limit is than low 28 times of the chemiluminescence method of having reported.
4. of the present invention novel
1O
2Fluorescence probe is right
1O
2Good selectivity is arranged, with other active oxygen species effect fluorescence signal no change almost.
Description of drawings
Fig. 1 is an europium complex
1O
2The structural formula of fluorescence probe;
Fig. 2 is the synthetic route of ligand ATTA;
Fig. 3 replaces 2,2 ': 6 ', 2 for containing anthracene nucleus "-synthetic route of ter cycloheptapyridine skeleton structure ligand;
Fig. 4 is ATTA-Eu
3+(solid line, 1.0 μ mol/L) and EP-ATTA-Eu
3+(dotted line, 1.0 μ mol/L) fluorescence spectrum in the 0.05mol/L of pH value 9.1 borate buffer solution;
Fig. 5 is EP-ATTA-Eu
3+(1.0 μ mol/L) fluorescence intensity (●) and fluorescence lifetime (zero) in the 0.05mol/L of different pH values Tris-HCl buffer solution;
Fig. 6 is EP-ATTA-Eu
3+(■) and the light stability experimental result of fluorescein () in the 0.05mol/L of pH value 9.1 borate buffer solution;
Fig. 7 is for using ATTA-Eu
3+Detect Na
2MoO
4/ H
2O
2Quantitatively produce in the system
1O
2Working curve.
Embodiment
The invention will be further described below by embodiment.
Synthetic route as shown in Figure 2, the matrix operating process is as follows.
(1) (E)-3-(9-anthryl)-1-(2 '-pyridine radicals)-2-propenone (compound 1) synthetic
10.31 gram 9-anthracene aldehyde (50mmol) and 2.81 gram KOH (50mmol) are mixed in the mixed solution that is dissolved in 200ml methyl alcohol and 40ml water composition; Stir after 30 minutes, slowly drip 6.06 gram 2-acetylpyridine (50mmol) in reaction system, stirred 24 hours under the room temperature; Filter collecting precipitation, thick product ethyl alcohol recrystallization; Get target compound 12.77 grams, productive rate: 82.6%.
1H NMR (CDCl
3) measurement result: δ=8.48-8.54 (m, 5H); 7.92 (m, 1H); 8.03 (d, J=8.4Hz, 2H); 8.27-8.31 (m, 2H); 8.37 (d, J=8.0Hz, 2H); 8.48 (s, 1H); 8.70 (d, J=4.4Hz, 1H); 8.93 (d, J=16.0Hz, 1H).
(2) 4 '-(9-anthryl)-2,2 ': 6 ', 2 "-ter cycloheptapyridine (compound 2) synthetic
Add 15.47 and digest compound 1,16.46 gram [2-(2 '-pyridine radicals)-2-oxoethyl] pyridine iodide (50mmol) and the dry ammonium acetate of 23.12 grams in the dry methyl alcohol of 500ml, reactant liquor refluxes and stirred 24 hours; Remove solvent under reduced pressure, residue 400ml chloroform extracting; Steam except that behind the chloroform, thick product separates with silica gel column chromatography, makees eluant, eluent with 2: 1 petroleum ether-ethyl acetate, collects second component; Product washs with acetonitrile, and vacuum drying gets target compound 5.48 grams, productive rate: 26.8%.
1H NMR (CDCl
3) measurement result: δ=7.26-7.37 (m, 4H); 7.47 (t, J=7.6Hz, 2H); 7.71 (d, J=8.8Hz, 2H); 7.92 (m, 2H); 8.07 (d, J=8.8Hz, 2H); 8.55 (s, 1H); 8.61 (s, 2H); 8.63 (d, J=4.0Hz, 2H); 8.79 (d, J=8.0Hz, 2H).Results of elemental analyses, calculated value: C 85.06%, H 4.68%, and N 10.26%; Measured value: C 84.66%, H 4.63%, and N 9.90%.
(3) 6,6 "-dinitrile-4 '-(9-anthryl)-2,2 ': 6 ', 2 "-ter cycloheptapyridine (compound 3) synthetic
3.3 m-chloro-benzoic acid peroxides (32.0mmol) that digest compound 2 (8.0mmol) and 6.9 grams 80% are dissolved in the 160ml methylene chloride, stirred 24 hours under the room temperature; The organic phase Na of 150ml 10%
2CO
3Solution washing twice behind the anhydrous sodium sulfate drying, removes solvent under reduced pressure, vacuum drying; With above-mentioned product that obtains and 6.34 gram Me
3SiCN (64.0mmol) is dissolved in 200ml CH
2Cl
2In, stir after 1 hour under the room temperature, slowly be added dropwise to 5.62 gram chlorobenzoyl chlorides (40.0mmol), stirred 24 hours under the room temperature; Remove solvent under reduced pressure, add 200ml 10%K
2CO
3Solution stirred 1 hour under the room temperature; Filter collecting precipitation, thick product washs with acetonitrile; Get target compound 2.34 grams, productive rate: 63.6%.
1H NMR (CDCl
3) measurement result: δ=7.40 (t, J=7.2Hz, 2H); 7.50 (t, J=8.0Hz, 2H); 7.63 (d, J=8.8Hz, 2H); 7.75 (d, J=7.2Hz, 2H); 8.05-8.12 (m, 4H); 8.61 (s, 1H); 8.72 (s, 2H); 8.98 (d, J=8.0Hz, 2H).
(4) 4 '-(9-anthryl)-2,2 ': 6 ', 2 "-ter cycloheptapyridine-6,6 "-dioctyl phthalate dimethyl ester (compound 4) synthetic
Digest compound 3 (4.1mmol) with 1.89 and be dissolved in the mixed solution that the 12ml concentrated sulphuric acid, 24ml glacial acetic acid and 6ml water is made into, 85-90 ℃ was stirred 12 hours down; Reactant liquor filters collecting precipitation, vacuum drying to going in the 500ml frozen water;
With 4.11 gram SOCl
2(34.6mmol) under ice bath, slowly join in the methyl alcohol of 125ml drying, stir after 20 minutes, add the said hydrolyzed product, stirring and refluxing 24 hours; Remove solvent under reduced pressure, add the Na of 100ml 10%
2CO
3In the solution, filter collecting precipitation, vacuum drying; Thick product separates with silica gel column chromatography, with 95: 5 chloroform-methanol wash-out, collects first component; Get target compound 1.56 grams, productive rate: 72.4%.
1H NMR (CDCl
3) measurement result: δ=3.90 (s, 6H); 7.36 (t, J=8.8Hz, 2H); 7.50 (t, J=7.2Hz, 2H); 7.66 (d, J=8.8Hz, 2H); 8.06-8.12 (m, 4H); 8.19 (d, J=8.0Hz, 2H); 8.61 (s, 1H); 8.73 (s, 2H); 8.99 (d, J=7.2Hz, 2H).
(5) 6,6 "-dihydroxymethyl 4 '-(9-anthryl)-2,2 ': 6 ', 2 "-ter cycloheptapyridine (compound 5) synthetic
Digest compound 4 (2.9mmol) with 1.52 and be dissolved in the 48ml absolute ethyl alcohol, stir and form suspension; Add 0.44 gram NaBH
4(11.6mmol) stirred 2 hours under the room temperature, reflux again and stirred 8 hours; Remove solvent under reduced pressure, add the saturated NaHCO of 8ml
3Solution is heated to and boils; The cooling back adds 60ml water, filters collecting precipitation, thick product water and acetonitrile washing, vacuum drying; Get target compound 1.02 grams, productive rate: 74.9%.
1H NMR (CDCl
3) measurement result: δ=4.74 (s, 4H); 7.25 (d, J=7.8Hz, 2H); 7.36 (t, J=7.8Hz, 2H); 7.48 (t, J=7.8Hz, 2H); 7.67 (d, J=8.0Hz, 2H); 7.90 (t, J=7.8Hz, 2H); 8.09 (d, J=8.8Hz, 2H); 8.58 (s, 1H); 8.60 (s, 2H); 8.68 (d, J=8.0Hz, 2H).
(6) 6,6 "-two bromomethyls-4 '-(9-anthryl)-2,2 ': 6 ', 2 "-ter cycloheptapyridine (compound 6) synthetic
In the 40ml dry DMF, add 1.21 gram PBr
3(4.5mmol), stir under the room temperature and add 0.84 after 15 minutes and digest compound 5 (1.8mmol), continue to stir 24 hours; Reaction finishes the back and adds saturated NaHCO
3Collecting precipitation is filtered in the solution neutralization, thick product water and acetonitrile washing, vacuum drying; Get target compound 0.83 gram, productive rate: 77.9%.
1H NMR (CDCl
3) measurement result: δ=4.52 (s, 4H); 7.38 (t, J=7.8Hz, 2H); 7.49 (m, 4H); 7.70 (d, J=7.8Hz, 2H); 7.92 (t, J=7.8Hz, 2H); 8.10 (d, J=8.0Hz, 2H); 8.59 (s, 1H); 8.65 (s, 2H); 8.70 (d, J=8.0Hz, 2H).
(7) 4 '-(9-anthryl)-2,2 ': 6 ', 2 "-Lian three pyrroles-6,6 "-dimethylamine tetraacethyl ethyl ester (compound 7) synthetic
Digest compound 6 (1mmol), 0.42 gram ethyl diacetate base amine (2.2mmol) and 1.38 gram anhydrous K with 0.60
2CO
3(10mmol) in the mixed solution that the tetrahydrofuran of the acetonitrile of adding 70ml drying and 21ml drying is made into, stirring and refluxing 24 hours; Remove by filter insolubles, remove solvent under reduced pressure; Product is dissolved in the 100ml chloroform, with the saturated NaHCO of equal volume
3And water washing.The organic phase anhydrous sodium sulfate drying removes under reduced pressure behind the solvent and separates with silica gel column chromatography, and eluent is petroleum ether-ethyl acetate-triethylamine of 2: 1: 0.3, collects first component; Remove a small amount of petroleum ether of product behind the solvent under reduced pressure, vacuum drying; Get target compound 0.55 gram, productive rate: 68.0%.
1H NMR (CDCl
3) measurement result: δ=1.07 (t, J=7.2Hz, 12H); 3.58 (s, 8H); 3.97-4.02 (m, 12H); 7.37 (t, J=8.0Hz, 2H); 7.48 (t, J=7.2Hz, 2H); 7.64 (d, J=8.0Hz, 2H); 7.72 (d, J=7.2Hz, 2H); 7.90 (t, J=8.0Hz, 2H); 7.72 (d, J=8.0Hz, 2H); 8.57 (s, 3H); 7.72 (d, J=8.0Hz, 2H).
(8) [4 '-(9-anthryl)-2,2 ': 6 ', 2 "-ter cycloheptapyridine-6,6 "-dimethylamine] tetraacethyl (ATTA) synthetic
Digest compound 7 (1.7mmol) with 1.39 and be dissolved in the mixed solution that 60ml ethanol and 10ml water is made into, add 2.02 gram KOH (36.0mmol) again, reflux and stirred 2 hours; After removing solvent under reduced pressure, product is dissolved in the 30ml water, with about 1: 1 hydrochloric acid adjust pH to 3, stirs 3 hours under the room temperature; Filter collecting precipitation, water, acetonitrile fully wash; Get target compound 0.81 gram, productive rate: 65.6%.
1H NMR (DMSO-d
6) measurement result: δ=3.45 (s, 8H); 3.96 (s, 4H); 7.47 (t, J=8.0Hz, 2H); 7.56-7.63 (m, 4H); 7.80 (d, J=8.0Hz, 2H); 8.08 (t, J=8.0Hz, 2H); 8.23 (t, J=8.0Hz, 2H); 8.43 (s, 2H); 8.69 (d, J=8.0Hz, 2H); 8.82 (s, 1H).Results of elemental analyses is pressed C
39H
33N
5O
81.5H
2O calculated value: C 64.64%, H 4.99%, and N 9.64%; Measured value: C 64.52%, H 5.38%, and N 9.30%.ESI-MS：m/z(％)：698(100)M
--H]。
Synthetic route as shown in Figure 3, the synthetic operation method is identical with embodiment 1.
With 36mg ATTA (0.05mmol) and 18mg EuCl
36H
2O (0.05mmol) is dissolved in the NaHCO of pH value 10.5
3In-NaOH the buffer solution, stir under the room temperature after 2 hours, add 1.2gNa
2MoO
42H
2O (5mmol) and 500 μ l30%H
2O
2, stirred again 30 minutes; The fluorescence intensity of observation reactant liquor changes, and continues to add H
2O
2, no longer change until the reactant liquor fluorescence intensity; With HCl the pH value of reactant liquor is transferred to about 3, is filtered collecting precipitation, washing final vacuum drying; ATTA-Eu
3+With
1O
2The inner oxide that reaction generates (is called for short EP-ATTA-Eu
3+) determine through ESI-MS: ESI-MS:m/z (%): 882 (10) [M
--H].
(1) fluorescence spectrum, fluorescence intensity and fluorescence lifetime
0.05mol/L sodium borate buffer solution with pH value 9.1 is that solvent has been measured ATTA-Eu
3+Uv-vis spectra in this solvent, fluorescence spectrum, molar extinction coefficient (ε), fluorescent quantum yield (φ) and fluorescence lifetime (τ).EP-ATTA-Eu
3+By ATTA-Eu
3+With Na
2MoO
4/ H
2O
20.1mol/LNaHCO in pH value 10.5
3Prepare in-NaOH the buffer solution, with after 10 times of the 0.05mol/L sodium borate buffer solution of pH value 9.1 dilutions, measure its photoluminescent property in this solvent again.It is a day beautiful UV7500 spectrophotometer that uv-vis spectra is measured with instrument.The fluorometric assay instrument is a Perkin Elmer LS 50B fluorospectrophotometer; Fluorescence quantum yield is measured and is used 4 '-phenyl-2,2 ': 6 ', 2 "-Lian three pyrroles-6; 6 " the complex of-dimethylamine tetraacethyl europium records (document 13:M.Latva, H.Takalo, V.M.Mukkala as reference material, C.Matachescu, J.C.Rodriguez-Ubis, J.Kankare, J.Lumin., 1997,75,149-169), calculating formula is φ
1=I
1ε
2C
2φ
2/ I
2ε
1C
1, I in the formula
2, ε
2, C
2, φ
2Be fluorescence intensity, molar extinction coefficient, concentration and the fluorescent quantum yield of reference material, I
1, ε
1, C
1, φ
1Fluorescence intensity, molar extinction coefficient, concentration and fluorescence quantum yield for determinand.
Measurement result sees Table 1.
Table 1.ATTA-Eu
3+And EP-ATTA-Eu
3+Absorption in sodium borate buffer solution and photoluminescent property
| Compound | Maximum absorption wavelength (nm) | Molar extinction coefficient, 335nm (mol -1Lcm -1) | Maximum fluorescence emission wavelength (nm) | Fluorescence quantum yield (%) | Fluorescence lifetime (ms) |
| ATTA-Eu 3+ | 294，335 | 17200 | 615 | 0.58 | 0.989 |
| EP-ATTA-Eu 3+ | 294，335 | 14500 | 615 | 10.0 | 1.209 |
By table 1 as seen, probe ATTA-Eu
3+With
1O
2Very big variation, ATTA-Eu have taken place in its fluorescence intensity before and after the reaction
3+Fluorescence is very weak, and EP-ATTA-Eu
3+Has very strong fluorescence.The fluorescence spectrum of two kinds of compounds as shown in Figure 4.
(2) the pH value of solution value is to EP-ATTA-Eu
3+The influence of photoluminescent property
With EP-ATTA-Eu
3+With the 0.05mol/L Tris-HCl buffer solution dissolving of different pH values, measure its fluorescence intensity and fluorescence lifetime under different pH values, it the results are shown in Figure 5; As seen from the figure, the pH value greater than 3 scope in, EP-ATTA-Eu
3+Fluorescence intensity and fluorescence lifetime be subjected to the influence of pH value little, show that this probe all can use in faintly acid, neutrality and weakly alkaline environment.
(3) EP-ATTA-Eu
3+Light stability
Respectively with fluorescein and EP-ATTA-Eu
3+Aqueous solution under the deuterium lamp of 30W, shone 65 minutes, every 5 minutes record first order fluorescence intensity, the result was as shown in Figure 6; EP-ATTA-Eu as seen from Figure 6
3+Have better light stability than fluoresceins probe, be applicable in the living things system more
1O
2The fluorescent microscope imaging measure.
At the 0.1mol/L of pH value 10.5 NaHCO
3Add ATTA-Eu in the-NaOH buffer solution respectively
3+(100nmol/L), Na
2MoO
4(10mmol/L) and the H of a series of concentration
2O
2(the H of per 2 molecules in this system
2O
2Produce 1 molecule
1O
2); Place after 18 hours down for 37 ℃ reactant liquor is carried out time-resolved fluorometry.Measuring with instrument is Wallac Victor 1420 multiple labeling calculating instruments (Perkin Elmer Life Sciences company products), and condition determination is: excitation wavelength, 340nm; Detect wavelength, 615nm; Time delay, 0.2ms; The window time, 0.4ms; Cycling time, 1.0ms.
As shown in Figure 7,
1O
2Amount and fluorescence intensity have good linear relationship, explanation
1O
2Can be by probe ATTA-Eu
3+Detection by quantitative.3 times with the background signal standard deviation are calculated minimum detectability, get ATTA-Eu
3+Right
1O
2Minimum detectability be 2.8nmol/L, lower 28 times than the chemiluminescence method of having reported.
Embodiment 6.ATTA-Eu
3+Right
1O
2Selectivity detect
Containing 100nmol/LATTA-Eu
3+The 0.1mol/L NaHCO of pH value 8.4
3 Add 10 μ mol/L H in the buffer solution respectively
2O
2, 10 μ mol/L H
2O
2With 10 μ mol/L iron ammonium sulfates (OH) and 10 μ mol/L KO
2(O
2 -), observe its change in fluorescence then; Probe ATTA-Eu
3+After the effect of above-mentioned active oxygen composition, fluorescence intensity has increased by 12%, 76% and 6% respectively, much smaller than
1O
2(increasing by 1246%) illustrates ATTA-Eu
3+Right
1O
2Has very high selectivity.
Claims (5)
1. a singlet oxygen europium coordination compound fluorescent probe is characterized in that: be with trivalent europium ion Eu
3+With contain functional groups 2,2 ': 6 ' 2 "-complex that ter cycloheptapyridine skeleton structure class ligand forms, wherein said ligand structure formula is:
R＝H，C
nH
2n+1，C
6H
5
2. according to the described singlet oxygen europium coordination compound fluorescent probe of claim 1, it is characterized in that: n=1～6 wherein.
3. the application of the described singlet oxygen europium coordination compound fluorescent probe of claim 1 is characterized in that: in all kinds of biologies and abiotic environment, utilize described europium coordination compound fluorescent probe to catch in the system
1O
2, make the fluorescence intensity of probe change greatly, then by fluorometry measure probe with
1O
2The variable quantity of fluorescence intensity is measured before and after the effect
1O
2Concentration, determine
1O
2Generation and growing amount.
Europium coordination compound fluorescent probe of the present invention can
4. according to the application of the described singlet oxygen europium coordination compound fluorescent probe of claim 3, it is characterized in that: described fluorometry is conventional fluorometry, time-resolved fluorometry or time-resolved fluorescence measurement microscope method.
5. according to the application of the described singlet oxygen europium coordination compound fluorescent probe of claim 1, it is characterized in that: be used to be prepared into and contain claim 1 described singlet oxygen europium coordination compound fluorescent probe
1O
2Detectable and kit.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277155A (en) * | 2011-06-28 | 2011-12-14 | 中国科学院福建物质结构研究所 | Preparation method and application of organic white light-emitting material L-COOH |
| CN102329264A (en) * | 2011-06-28 | 2012-01-25 | 中国科学院福建物质结构研究所 | Preparation and application of organic white light emitting material L-Cl |
| CN102732246A (en) * | 2012-06-15 | 2012-10-17 | 大连理工大学 | Europium complex singlet oxygen fluorescent probe with cell membrane permeability and its application |
| CN105566363A (en) * | 2016-01-04 | 2016-05-11 | 辽宁大学 | Rare earth coordination polymer based on tripod flexible ligand, preparation method and applications thereof |
| CN105917215A (en) * | 2013-11-19 | 2016-08-31 | 凯米罗总公司 | Method for analysing a sample comprising at least a first and a second scale inhibitor |
| CN111693500A (en) * | 2020-06-19 | 2020-09-22 | 哈尔滨工业大学 | Method for realizing monitoring of singlet oxygen quantum yield based on time-resolved spectral measurement |
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2005
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102277155A (en) * | 2011-06-28 | 2011-12-14 | 中国科学院福建物质结构研究所 | Preparation method and application of organic white light-emitting material L-COOH |
| CN102329264A (en) * | 2011-06-28 | 2012-01-25 | 中国科学院福建物质结构研究所 | Preparation and application of organic white light emitting material L-Cl |
| CN102277155B (en) * | 2011-06-28 | 2014-10-15 | 中国科学院福建物质结构研究所 | Preparation method and application of organic white light-emitting material L-COOH |
| CN102329264B (en) * | 2011-06-28 | 2015-03-04 | 中国科学院福建物质结构研究所 | Preparation and application of organic white light emitting material L-Cl |
| CN102732246A (en) * | 2012-06-15 | 2012-10-17 | 大连理工大学 | Europium complex singlet oxygen fluorescent probe with cell membrane permeability and its application |
| CN105917215A (en) * | 2013-11-19 | 2016-08-31 | 凯米罗总公司 | Method for analysing a sample comprising at least a first and a second scale inhibitor |
| US10241047B2 (en) | 2013-11-19 | 2019-03-26 | Kemira Oyj | Method for analysing a sample comprising at least a first and a second scale inhibitor |
| CN105917215B (en) * | 2013-11-19 | 2019-05-31 | 凯米罗总公司 | For analyzing the method comprising at least sample of the first and second antisludging agents |
| CN105566363A (en) * | 2016-01-04 | 2016-05-11 | 辽宁大学 | Rare earth coordination polymer based on tripod flexible ligand, preparation method and applications thereof |
| CN111693500A (en) * | 2020-06-19 | 2020-09-22 | 哈尔滨工业大学 | Method for realizing monitoring of singlet oxygen quantum yield based on time-resolved spectral measurement |
| CN111693500B (en) * | 2020-06-19 | 2022-11-25 | 哈尔滨工业大学 | Method for realizing monitoring of singlet oxygen quantum yield based on time-resolved spectral measurement |
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