CN108586260A - A kind of fluorescence probe of detection sulphur hydrogen radical and preparation method and application - Google Patents
A kind of fluorescence probe of detection sulphur hydrogen radical and preparation method and application Download PDFInfo
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- 239000000523 sample Substances 0.000 title claims abstract description 34
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 title claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000005864 Sulphur Substances 0.000 title claims abstract description 18
- 238000001514 detection method Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 17
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 5
- 229940125904 compound 1 Drugs 0.000 claims description 5
- 229940125782 compound 2 Drugs 0.000 claims description 5
- 238000002189 fluorescence spectrum Methods 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003068 molecular probe Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- UOYPNWSDSPYOSN-UHFFFAOYSA-N hexahelicene Chemical compound C1=CC=CC2=C(C=3C(=CC=C4C=CC=5C(C=34)=CC=CC=5)C=C3)C3=CC=C21 UOYPNWSDSPYOSN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical class OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 claims 1
- 150000001450 anions Chemical class 0.000 abstract description 11
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 abstract description 4
- 241000370738 Chlorion Species 0.000 abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 4
- 108010024636 Glutathione Proteins 0.000 abstract description 4
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 abstract description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 abstract description 4
- 235000018417 cysteine Nutrition 0.000 abstract description 4
- 229960003180 glutathione Drugs 0.000 abstract description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 abstract description 4
- 229940006461 iodide ion Drugs 0.000 abstract description 4
- 229940005654 nitrite ion Drugs 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- FFFHZYDWPBMWHY-VKHMYHEASA-N L-homocysteine Chemical compound OC(=O)[C@@H](N)CCS FFFHZYDWPBMWHY-VKHMYHEASA-N 0.000 abstract description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 abstract description 2
- 229940006460 bromide ion Drugs 0.000 abstract description 2
- 229960002433 cysteine Drugs 0.000 abstract description 2
- 150000003573 thiols Chemical class 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- -1 glycol dimethyl ethers Chemical class 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- NMOJAXCSURVGEY-UHFFFAOYSA-N N#CC#N.[S] Chemical compound N#CC#N.[S] NMOJAXCSURVGEY-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 0 CCCC*C(c(c(COCCCC)c1CCc2c3)c(CCc(c-4c5)cc(-c(cc6)ccc6Oc(c([N+]([O-])=O)c6)ccc6[N+]([O-])=O)c5OC)c-4c1-c2cc(OC)c3-c(cc1)ccc1Oc(c([N+]([O-])=O)c1)ccc1[N+]([O-])=O)=* Chemical compound CCCC*C(c(c(COCCCC)c1CCc2c3)c(CCc(c-4c5)cc(-c(cc6)ccc6Oc(c([N+]([O-])=O)c6)ccc6[N+]([O-])=O)c5OC)c-4c1-c2cc(OC)c3-c(cc1)ccc1Oc(c([N+]([O-])=O)c1)ccc1[N+]([O-])=O)=* 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 201000010374 Down Syndrome Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 208000037273 Pathologic Processes Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 206010044688 Trisomy 21 Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007812 electrochemical assay Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000009054 pathological process Effects 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
- C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
- C07C205/38—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. nitrodiphenyl ethers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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"
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- 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
- G01N21/6447—Fluorescence; Phosphorescence by visual observation
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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Abstract
The invention discloses a kind of fluorescence probe and its preparation method and application of detection sulphur hydrogen radical ion, the molecular formula of the probe is：C56H46N4O16, structural formula are as follows：
Description
【Technical field】
The invention belongs to the molecular probe fields of ion detection, especially a kind of molecule for selective enumeration method sulphur hydrogen radical
Probe and the preparation method and application thereof.
【Background technology】
Hydrogen sulfide is a kind of inflammable sour gas, colourless, and there is rotten egg smell in when low concentration.Hydrogen sulfide can cause to exhale
The stimulation for inhaling road and eyes, causes to have a headache sometimes.It has recently been demonstrated that endogenic hydrogen sulfide gas is after nitric oxide
With the third gaseous signal molecule after carbon monoxide, play an important role in a variety of physiology and pathologic process.However, working as
When concentration of hydrogen sulfide is more than normal level in organism, may result in various health problems, for example, Alzheimer's disease and
Down's syndrome etc..Therefore, it realizes and research hotspot is had become to the convenience of hydrogen sulfide, Selective recognition, attract wide attention.
So far, there are many method of detection sulphur hydrogen radical, including colorimetric analysis, electrochemical assay, sulfide precipitation are gentle
Phase chromatography etc..But these method expensive equipments, processing is complicated, cannot monitor in real time, has significant limitation.And fluorescence
Ion existence information can be converted into the optical signal being easily detected by method, and detection limit is low, convenience and high-efficiency, can monitor in real time,
It is widely used in analyzing detection field.
【Invention content】
The purpose of the present invention is analyzing in view of the above technology and there are problem, a kind of fluorescence probe and its preparation side are provided
Method, and its application in sulphur hydrogen radical ion detection.
Technical scheme of the present invention：
A kind of fluorescent molecular probe of detection sulphur hydrogen radical ion, the molecular formula of the probe are：C56H46N4O16, structure
It is as follows：
Preparation method described above for detecting the fluorescence probe of sulphur hydrogen radical ion, steps are as follows：
(1) under inert gas shielding, hydrogenation helicene compound 1, nothing is added in the in the mixed solvent of glycol dimethyl ether and water
Aqueous carbonate potassium, 4- hydroxyls phenyl boric acid, tetra-triphenylphosphine palladium, are heated to reflux.It is extracted with ethyl acetate after reaction, vacuum is dry
Dry, column chromatography method purifies to obtain compound 2.
(2) under inert gas shielding, compound 2,2,4-dinitrochlorobenzene are added in ethanol solution, appropriate anhydrous carbon is added
Sour potassium is stirred at room temperature as alkali.Column chromatography method purifies to obtain probe molecule I.
Wherein reaction described in step (1) need to carry out under inert gas protection；
The use of the compound 1, Anhydrous potassium carbonate, 4- hydroxyls phenyl boric acid, tetra-triphenylphosphine palladium, glycol dimethyl ether and water
Amount is than being 1mol:5-15mol:2-10mol:0.02-0.1mol:5-25L:5-25L, concretely 1mol:5-10mol:2-
5mol:0.02-0.05mol:5-15L:5-15L
Reaction described in step (2) need to carry out under inert gas protection；
The amount ratio of the compound 2,1-CHLORO-2,4-DINITROBENZENE and Anhydrous potassium carbonate is 1mol:2-8mol:3-10mol,
Concretely 1mol:2-5mol:3-6mol
The study found that the fluorescence probe application method of the present invention is not particularly limited, it usually can be at room temperature by probe point
Sub- I is dissolved in the mixed solution of DMSO and water and is tested, when sulphur hydrogen radical ion is added, since sulphur hydrogen radical ion can destroy
Ehter bond so that the PET effects of intramolecular are suppressed, and cause ultraviolet spectra and fluorescence spectrum that significant change occurs, and naked eyes are visible molten
Liquid becomes brown color from colourless, while yellow-green fluorescence occurs.
It is an advantage of the invention that：Fluorescence probe I prepared by the present invention, synthesis is simple and convenient, and yield is high, easily prepared, fits
In amplification synthesis and production application.UV, visible light method and fluorescent method can be utilized to detect sulphur hydrogen radical ion.Selection
Property it is good, detection speed is fast, and be suitble to open hole detection, not by acetate ion, thiocyanate ion, nitrite ion, nitre
Acid ion, sulfate ion, bicarbonate ion, fluorine ion, chlorion, bromide ion, iodide ion, cysteine, high half Guang
The interference of the anion such as propylhomoserin, glutathione and biological thiol.It can be applied to ion detection field as novel probe,
It has broad application prospects.
【Description of the drawings】
Fig. 1 is that the ultra-violet absorption spectrum after 40 equivalent different anions and compounds containing thiol groups is added in probe I solution.
Fig. 2 is that the fluorescence spectrum after 40 equivalent different anions and compounds containing thiol groups is added in probe I solution.
【Specific implementation mode】
In order to further illustrate the present invention, following serial specific embodiment is provided, but the present invention is not specific real by these
The limitation of example is applied, understanding person skilled in art will can reach similar as a result, these change to the few modifications of the present invention
It is dynamic to be also included in the present invention.
Embodiment 1：The preparation of fluorescence probe I
(1) Anhydrous potassium carbonate (0.157g, 1.14mmol), 4- hydroxy benzenes boron is added in compound 1 (76mg, 0.114mmol)
Sour (47.17mg, 0.342mmol), 15mL glycol dimethyl ethers, 10mL water, 13mg tetra-triphenylphosphine palladiums under nitrogen protection, add
Heat reflux 12 hours.After be extracted with ethyl acetate, column chromatography method purifying, obtain compound 2 (66mg, 82%).
(2) 2,4-dinitrochlorobenzene (0.25g, 1.24mmol), anhydrous carbon is added in compound 2 (0.3g, 0.413mmol)
Sour potassium (0.28g, 1.25mmol), acetonitrile 20mL are stirred at room temperature 8 hours under nitrogen protection.It purifies to obtain fluorescence by column chromatography
Probe I (0.32g, 75%).
Testing result：
1H NMR(500MHz,CDCl3) δ 8.88 (s, 1H), 8.35 (d, J=8.0Hz, 1H), 7.66 (d, J=7.8Hz,
2H), 7.29 (d, J=9.7Hz, 1H), 7.17 (t, J=9.5Hz, 3H), 6.80 (s, 1H), 4.34 (d, J=29.4Hz, 2H),
3.38 (d, J=22.4Hz, 3H), 3.11 (m, 1H), 2.89 (m, 2H), 2.74 (s, 1H), 1.75 (m, 2H), 1.48 (m, 2H),
0.99 (t, J=6.9Hz, 3H)
13C NMR(126MHz,CDCl3)δ168.23,156.24,153.91,152.59,141.44,139.56,
137.72,136.48,135.15,134.24,131.77,131.60,130.19,129.51,129.09,128.86,128.41,
128.28,122.22,120.17,118.67,114.12,65.73,55.20,30.63,28.16,27.80,19.35,13.85.
Embodiment 2：The application of sulfurous acid hydrogen radical ion fluorescence probe.
Molecular probe I is dissolved in dimethyl sulfoxide (DMSO), the probe solution of 1mmol/L is configured to, and be diluted to DMSO and
Mixed solution (the DMSO of PBS buffer solution：PBS=9:1, v/v), with ultraviolet-uisible spectrophotometer and sepectrophotofluorometer pair
Probe I identifies HSO3 -Performance studied.A concentration of the 1 × 10 of probe I-5M and 5 × 10-6M is respectively intended to carry out ultraviolet
It absorbs and fluorescence spectrum is tested.
Fig. 1 is that the ultra-violet absorption spectrum after 40 equivalent different anions and compounds containing thiol groups is added in probe I solution.
1×10-5In the probe I solution of M, it is separately added into the different anion of 40 equivalents and sulfhydryl compound (acetate ion, sulphur cyanogen
Acid ion, nitrite ion, nitrate ion, sulfate ion, bicarbonate ion, fluorine ion, chlorion, bromine from
Son, iodide ion, cysteine, homocysteine, glutathione).It was found that probe molecule I is after being added sulphur hydrogen radical ion,
UV absorption intensity is decreased obviously at 300nm-350nm, and ultraviolet absorption peak obviously rises at 455nm, and solution becomes palm fibre from colourless
Yellow.Other anion and sulfhydryl compound, which are added, does not have significant change.
Fig. 2 is that the fluorescence spectrum after 40 equivalent different anions and compounds containing thiol groups is added in probe I solution.5×
10-6In the solution of the probe I of M, it is separately added into the different anion of 40 equivalents and sulfhydryl compound (acetate ion, sulphur cyanogen
Acid ion, nitrite ion, nitrate ion, sulfate ion, bicarbonate ion, fluorine ion, chlorion, bromine from
Son, iodide ion, cysteine, homocysteine, glutathione).It selects 380nm wavelength lights as exciting light, finds probe I sheet
Body almost unstressed configuration in the solution, however after sulphur hydrogen radical ion is added, occur new fluorescence emission peak at 520nm, is strong
Yellow-green fluorescence.Other anion and sulfhydryl compound, which are added, does not have significant change.
The result shows that the fluorescence probe I of synthesis has good responding ability for sulphur hydrogen radical, while can avoid common
The interference of compounds containing thiol groups in anion and organism can be used as colorimetric and fluorescence probe selectively to detect sulphur hydrogen
Radical ion has wide practical use.
Claims (6)
1. a kind of fluorescent molecular probe of detection sulfurous acid hydrogen radical ion, the molecular formula of the probe are：C56H46N4O16, knot
Structure is as follows：
2. a kind of preparation method of compound as described in claim 1,
It is characterized by comprising following step：
(1) under inert gas shielding, hydrogenation helicene compound 1, anhydrous carbon is added in the in the mixed solvent of glycol dimethyl ether and water
Sour potassium, 4- hydroxyls phenyl boric acid, tetra-triphenylphosphine palladium, are heated to reflux.It is extracted with ethyl acetate, is dried in vacuo, column after reaction
Chromatography method purifies to obtain compound 2.
(2) under inert gas shielding, 2,4-dinitrochlorobenzene, compound 2 are added in ethanol solution, Anhydrous potassium carbonate, room temperature is stirred
It mixes.Column chromatography method purifies to obtain probe molecule I.
3. according to the method described in claim 2, it is characterized in that：Wherein reaction described in step (1) need to be protected in inert gas
Shield is lower to be carried out；The compound 1, Anhydrous potassium carbonate, 4- formylphenylboronic acids, tetra-triphenylphosphine palladium, glycol dimethyl ether and water
Amount ratio be 1mol:5-15mol:2-10mol:0.02-0.1mol:5-25L:5-25L, concretely 1mol:5-10mol:
2-5mol:0.02-0.05mol:5-15L:5-15L。
4. according to the method described in claim 2, it is characterized in that：Reaction described in step (2) needs under inert gas protection
It carries out；The amount ratio of the compound 2,1-CHLORO-2,4-DINITROBENZENE and Anhydrous potassium carbonate is 1mol:2-8mol:3-10mol, specifically
Can be 1mol:2-5mol:3-6mol.
5. a kind of application of fluorescence probe as described in claim 1, which is characterized in that the fluorescence probe can utilize fluorescence spectrum
Instrument detects sulphur hydrogen radical ion.
6. a kind of fluorescence probe as described in claim 1 is used for the application of open hole detection sulphur hydrogen radical ion.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170268997A1 (en) * | 2014-08-21 | 2017-09-21 | The University Of Utah Research Foundation | Chemical probes for hydrogen sulfide |
| CN107501221A (en) * | 2017-09-05 | 2017-12-22 | 中国科学院合肥物质科学研究院 | It is a kind of to fluorescence probe of hydrogen sulfide quick response and its production and use in organism |
| CN107760298A (en) * | 2017-09-28 | 2018-03-06 | 青岛科技大学 | A kind of fluorescence probe for detecting bisulfite and preparation method and application |
-
2018
- 2018-04-17 CN CN201810343700.9A patent/CN108586260A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170268997A1 (en) * | 2014-08-21 | 2017-09-21 | The University Of Utah Research Foundation | Chemical probes for hydrogen sulfide |
| CN107501221A (en) * | 2017-09-05 | 2017-12-22 | 中国科学院合肥物质科学研究院 | It is a kind of to fluorescence probe of hydrogen sulfide quick response and its production and use in organism |
| CN107760298A (en) * | 2017-09-28 | 2018-03-06 | 青岛科技大学 | A kind of fluorescence probe for detecting bisulfite and preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| MENG LI,等: "Tetrahydro[5]helicene-Based Nanoparticles for Structure-Dependent Cell Fluorescent Imaging", 《ADVANCED FUNCTIONAL MATERIALS》 * |
| 刘晓东: "有机小分子荧光探针的合成及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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