CN108148087A - Long wavelength's hydrogen peroxide fluorescence probe - Google Patents
Long wavelength's hydrogen peroxide fluorescence probe Download PDFInfo
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- CN108148087A CN108148087A CN201810155915.8A CN201810155915A CN108148087A CN 108148087 A CN108148087 A CN 108148087A CN 201810155915 A CN201810155915 A CN 201810155915A CN 108148087 A CN108148087 A CN 108148087A
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title abstract description 97
- 239000000523 sample Substances 0.000 title abstract description 54
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 125000003545 alkoxy group Chemical group 0.000 claims description 17
- -1 methoxyl group Chemical group 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 9
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 229960002163 hydrogen peroxide Drugs 0.000 description 40
- 239000000243 solution Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000007995 HEPES buffer Substances 0.000 description 6
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- 102000016938 Catalase Human genes 0.000 description 3
- 108010053835 Catalase Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000004060 metabolic process Effects 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- QDMCHWCVLPVAES-UHFFFAOYSA-N 2-benzylbenzaldehyde Chemical compound O=CC1=CC=CC=C1CC1=CC=CC=C1 QDMCHWCVLPVAES-UHFFFAOYSA-N 0.000 description 2
- ZZPNDIHOQDQVNU-UHFFFAOYSA-N 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(O)OC1(C)C ZZPNDIHOQDQVNU-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 210000004185 liver Anatomy 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- KWGACYZYFZTYRN-UHFFFAOYSA-N OC(C)(C)C(C)(C)O.B(O)(O)O.BrCC1=CC=CC=C1 Chemical class OC(C)(C)C(C)(C)O.B(O)(O)O.BrCC1=CC=CC=C1 KWGACYZYFZTYRN-UHFFFAOYSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 210000005229 liver cell Anatomy 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000007170 pathology Effects 0.000 description 1
- 230000004962 physiological condition Effects 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- KCDXJAYRVLXPFO-UHFFFAOYSA-N syringaldehyde Chemical compound COC1=CC(C=O)=CC(OC)=C1O KCDXJAYRVLXPFO-UHFFFAOYSA-N 0.000 description 1
- COBXDAOIDYGHGK-UHFFFAOYSA-N syringaldehyde Natural products COC1=CC=C(C=O)C(OC)=C1O COBXDAOIDYGHGK-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
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- Life Sciences & Earth Sciences (AREA)
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- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The present invention relates to long wavelength's hydrogen peroxide fluorescence probes.The probe of the present invention can act on, and have the characteristics that high sensitivity and selectivity with hydrogen peroxide, can be applied in hydrogen peroxide high sensitivity and highly selective identification or its can in determination sample hydrogen peroxide concentration.
Description
Technical field
The present invention relates to the long-wavelength fluorescent probes of detection hydrogen peroxide.The probe of the present invention can be made with hydrogen peroxide
With, and there is high sensitivity and selectivity, can be applied in hydrogen peroxide high sensitivity and highly selective identification or
Person its can in determination sample hydrogen peroxide concentration.
Background technology
Organism can generate H during respiratory metabolism is carried out2O2, hydrogen peroxide group is commonly called as " free radical ", by " mistake
The generation of hydrogen oxide enzyme " catalysis biological vivo protein group.Internal hydrogen peroxide is to be hydrolyzed to generate by hydrogen peroxide group
's.
This substance has the high oxidisability of comparison, can injure normal bio macromolecular such as protein and DNA etc. in cell.
Catalase is the enzyme that catalyzing hydrogen peroxide resolves into oxygen and water, is present in the peroxide body of cell, can be by H2O2
H is catalytically decomposed into2O and O2, it is harmless.Catalase is present in each tissue of all known animals, especially exists
Exist in liver with high concentration.This is because liver is chemical plant maximum in human body, it is removing toxic substances organ maximum in animal body,
A large amount of local behavior metabolism is carried out, generates H2O2Speed quickly, hydrogen peroxide be generated in a kind of metabolic process it is useless
Object, it can damage body.In order to avoid this damage, hydrogen peroxide must be rapidly converted into other it is harmless or
The smaller substance of toxicity.Catalase is present in the peroxidating body in red blood cell and certain tissues, its main function is just
It is catalysis H2O2It is decomposed into H2O and O2.So need high-strength hydrogen peroxide enzyme work protection liver cell.Hydrogen peroxide is as oxygen
Change stress a typical characteristics, balance physiology and pathology are had a major impact.The changes of contents of intracellular hydrogen peroxide and
The generation of many diseases has direct relationship, for example, cancer, diabetes, angiocardiopathy, neuratorphy disease etc..
Therefore, develop a kind of method for the content that can effectively quantitative determine the hydrogen peroxide bio molecule in organism
It is necessary.In numerous determination techniques, fluorescence probe is received significant attention due to the advantages of it is unique, including highly sensitive
Degree, specific selectivity and the advantages that real-time in-situ imaging analysis, thus design and synthesize one being capable of Quantitative detection life
The fluorescence probe of hydrogen peroxide molecule in object is all valuable for academic research and clinical practice.
At present, quantitatively the method for detection hydrogen peroxide has very much, mainly includes：Titration, fluorescence analysis, chemiluminescence
Method, colorimetric analysis method, emission spectrometry method, electrochemical method, chromatography of ions etc..Compared with other methods, fluorescence
Probe have in it advantage, including high sensitivity, specificity is implemented simple, and response quickly can realize real-time detection, can answer
For bio-imaging etc..And in terms of the fluorescence probe of detection hydrogen peroxide, there are many Fluorescence Increasing probe, but ratio probes are non-
Often few, ratio probes are compared with Fluorescence Increasing probe because that can eliminate environment to probe in detecting by the ratio between two peaks
Influence, so there is the application value of bigger.Therefore, developing one has larger mobile wavelength and can detect in physiological conditions
The fluorescence probe of hydrogen oxide is necessary.
Invention content
A kind of high sensitivity and the highly selective method for measuring hydrogen peroxide are badly in need of in this field, so as to effectively detect spy
It is not that can detect hydrogen peroxide in the sample.For this purpose, the present invention proposes a kind of method of novel detection hydrogen peroxide,
Required probe can be used directly, and not need to do further organic synthesis modification, and being capable of highly sensitive and highly selective identification peroxide
Change hydrogen.Probe of the present invention can be to hydrogen peroxide carry out high sensitivity and highly selective measure.
Specifically, the present invention provides a kind of probe for identifying hydrogen peroxide, structure is as follows：
Wherein：R1, R2, R3, R4, R5And R6For independently selected from by hydrogen atom, linear or branched alkyl group, linear chain or branch chain alkane
The group that oxygroup, sulfonic group, ester group and hydroxyl form；And R therein1, R2, R3, R4, R5And R6It can be identical or different.
Preferably, heretofore described linear or branched alkyl group, straight or branched alkoxyl are the alkyl or alcoxyl of C1-10
Base.
Preferably, heretofore described linear or branched alkyl group, straight or branched alkoxyl are the alkyl or alcoxyl of C1-5
Base.
Preferably, heretofore described linear or branched alkyl group, straight or branched alkoxyl are the alkyl or alcoxyl of C1-3
Base.
Preferably, heretofore described linear or branched alkyl group for methyl, ethyl, propyl, n-pentyl, 2- methyl butyls,
Isobutyl group or 4- methylheptyls.
Preferably, heretofore described straight or branched alkoxyl is methoxyl group, ethyoxyl or propoxyl group.
Preferably, R in the present invention1, R2, R3, R4, R5And R6Independently selected from hydrogen atom, methyl, ethyl, propyl, methoxy
Base, ethyoxyl or propoxyl group.
Preferably, probe of the invention is：
Description of the drawings
Fig. 1：Pure probe (10 μM) solution and the solution after probe (10 μM) solution and hydrogen peroxide (50 μM) hybrid reaction
The absorption spectrum of two groups of solution.
Fig. 2：Fluorescence emission spectrum, test system are pure aquatic system, 10mM containing HEPES, pH=7.4, CTAB 1mM,
Test temperature is 25 DEG C.
Fig. 3：Probe is for the H of various concentration2O2There is good response.Test system is pure aquatic system, containing HEPES
10mM, pH=7.4, CTAB 1mM, test temperature are 25 DEG C.Concentration and probe concentration is 10 μM, the concentration of hydrogen peroxide is followed successively by 1,2,
4th, it 6,8,10,15,20,25,30,35,40,50,60,70,80,90,100,150,200 μM, places 20 minutes and surveys after addition
.
Fig. 4：Probe has linear well at a concentration of 0-10 μM.Test system is pure aquatic system, containing HEPES
10mM, pH=7.4, CTAB 1mM, test temperature are 25 DEG C.Concentration and probe concentration is 10 μM, the concentration of hydrogen peroxide is followed successively by 1,2,
4th, 6,8,10,15,20,25,30,35,40,50,60,70,80,90,100,150,200 μM of reactions are put into fluorescence point after twenty minutes
Light photometer is detected gained.
Fig. 5：In other blank (NONE), TBHP, KO2、NaClO、ONOO-、·OH、·TBHP、H2O2A concentration of 50 μM or
In the absence of, probe (10 μM) is to the fluorescence response value of hydrogen peroxide.Test system is pure aquatic system, 10mM containing HEPES,
PH=7.4, CTAB 1mM, test temperature are 25 DEG C.
Specific embodiment
The present invention provides a kind of highly sensitive and highly selective fluorescence probes and its spectrum property for measuring hydrogen peroxide.
The probe of the present invention has following structure general formula：
Wherein：R1, R2, R3, R4, R5And R6For independently selected from by hydrogen atom, linear or branched alkyl group, linear chain or branch chain alkane
The group that oxygroup, sulfonic group, ester group and hydroxyl form；And R therein1, R2, R3, R4, R5And R6It can be identical or different.Preferably,
Heretofore described linear or branched alkyl group, straight or branched alkoxyl are the alkyl or alkoxy of C1-10.
Preferably, heretofore described linear or branched alkyl group, straight or branched alkoxyl are the alkyl or alcoxyl of C1-5
Base.
Preferably, heretofore described linear or branched alkyl group, straight or branched alkoxyl are the alkyl or alcoxyl of C1-3
Base.
Preferably, heretofore described linear or branched alkyl group for methyl, ethyl, propyl, n-pentyl, 2- methyl butyls,
Isobutyl group or 4- methylheptyls.
Preferably, heretofore described straight or branched alkoxyl is methoxyl group, ethyoxyl or propoxyl group.
Preferably, R in the present invention1, R2, R3, R4, R5And R6Independently selected from hydrogen atom, methyl, ethyl, propyl, methoxy
Base, ethyoxyl or propoxyl group.
Preferably, R in the present invention1, R2, R3, R4, R5And R6Independently selected from hydrogen, methyl, ethyl or propyl；Most preferably
Ground, R1, R2, R3, R4, R5And R6It is H.
It below will be by the way that the present invention be described in more detail by following embodiment.Following embodiment is merely illustrative,
It should be understood that the present invention is not limited by following embodiments.
It is prepared by 1 probe of embodiment
Synthesis of the 3,5- dimethyl -4- to boric acid pinacol ester benzyl benzaldehyde
It weighs 4- bromomethyl benzene boric acid pinacol esters 380mg to be put into 250mL flasks, adds in 120mL acetonitriles, then add in
The syringaldehyde of 200mg, is heated to reflux, and stops reaction after 6 hours.
Solution after reaction is added dropwise to liquid-phase chromatographic column, uses dichloromethane：Petroleum ether=10：3 solvent flushing liquor
Phase chromatographic column obtains purer product.
It will be put into round-bottomed flask by the product that chromatographic column obtains, add in dichloromethane as few as possible and dissolved,
And surpass ten minutes in supersonic cleaning machine, petroleum ether is then slowly added dropwise into solution, is rocked when being added dropwise, treats dichloromethane solution
In stop that petroleum ether is added dropwise when have a crystalline state precipitation.Then a funnel and beaker are taken, be fixed and with vacuum pump phase
Even, filter paper is put into wetting, substance is added dropwise and is filtered on filter paper, substance is transferred in round-bottomed flask with spoon after draining,
Dichloromethane dissolving is added in, solution is spin-dried for Rotary Evaporators, finally obtains pure substance.
The synthesis and purification of probe TCF- boron esters：
3, the 5- dimethyl -4- for weighing 300mg synthesis react boric acid pinacol ester benzyl benzaldehyde with 200mg nitriles,
100mL ethyl alcohol and two panels piperazine are added in, is reacted with masking foil package shading, stops reaction after 5 hours.
After reaction stops, observation solution is become the canescence after reaction by light yellow before reacting, is inhaled substance with dropper
It takes, filters, cleaned and filtered with ethyl alcohol, obtain purer probe TCF- boron esters.
The analysis of product structure characterization result：
1The analysis of H-NMR results：
1H-NMR(400MHz,DMSO-d6)δ(*10-6):1.30(s,12H),1.82(s,6H),3.87(s,6H),3.444
(s, 3H), 5.06 (s, 2H), 7.19 (d, J=16Hz, 1H), 7.27 (s, 2H), 7.46 (d, J=8Hz, 2H), 7.67 (d, J=
8Hz, 2H), 7.84 (d, J=16Hz, 1H).Data above meets the structural formula feature of probe TCF- boron esters.
Carbon composes the analysis of result：
13C-NMR(100MHz,DMSO-d6)δ(*10-6):19.03,25.16,25.72,56.49,56.77,74.30,
84.12,99.76,107.69,115.11,127.66,130.48,134.76,140.48,141.24,148.30,153.77,
175.71,177.65。
Embodiment 2：The absorption spectrum and fluorescence emission spectrum of probe
The probe mother liquor of 1mM is prepared first, and prepares the hydrogen peroxide mother liquor of 10mM.On the basis of mother liquor, 50 μ are prepared
The probe solution of M, then prepare the mixed solution that probe solution contains hydrogen peroxide (50 μM).Solution system in colorimetric cylinder is
Pure aquatic system, 10mM containing HEPES, pH=7.4, CTAB 1mM.Then, solution is used into ultraviolet specrophotometer and fluorescence respectively
Spectrophotometer measurement absorption spectrum and fluorescence emission spectrum simultaneously keep a record, and test temperature is 25 DEG C.As a result such as Fig. 1 and Fig. 2 institutes
Show.
Ultra-violet absorption spectrum as shown in Figure 1, find out that pure probe there is no absorption peak at 640nm from spectrogram, but
After hydrogen peroxide addition, a very strong absorption peak is produced at 640nm, absorption intensity enhances clearly.
Fluorescence emission spectrum from spectrogram as shown in Fig. 2, see that pure probe, substantially without peak, was adding at 660nm
After hydrogen oxide, apparent variation has occurred in spectrogram, and peak of the substance after reaction at 660nm gradually increases.
Embodiment 3：Probe is to the quantitative effect of hydrogen peroxide
10 μM of probe solution is prepared, is transferred in colorimetric cylinder, calibration is accurate.Hydrogenperoxide steam generator is taken to add in colorimetric
Guan Zhong, the concentration for making hydrogen peroxide are finally：1、2、4、6、8、10、15、20、25、30、35、40、50、60、70、80、90、
100th, it 150,200 μM and is rocked uniformly, test system is pure aquatic system, 10mM containing HEPES, pH=7.4, CTAB
1mM, recording light spectrogram simultaneously preserve.Test temperature is 25 DEG C.Placing response is after ten minutes with its hair of fluorescence spectrophotometer measurement
Spectrum is penetrated, record and is preserved.As a result as shown in Figure 3 and Figure 4.
Concentration and probe concentration is 10 μM, and along with gradually increasing for concentration of hydrogen peroxide, the emission peak at 660nm gradually increases
Height, as shown in figure 3, probe has good response for the hydrogen peroxide of various concentration, as shown in figure 4, a concentration of 0 to 35
μM when have it is linear well.These results all represent that our probe can pass through the detection of the method quantitative and qualitative of fluorescence
Hydrogen oxide simultaneously has certain sensitivity.
Embodiment 4：Research about probe Selective recognition hydrogen peroxide
10 μM of probe solution 200mL is prepared, probe solution is moved into constant volume in 16 colorimetric cylinders respectively, colorimetric cylinder is pressed
According to being sequentially placed on rack for test tube, be divided into front and rear two batches, before eight colorimetric cylinders, behind eight colorimetric cylinders, then by blank,
TBHP, KO2, NaClO, ONOO-, OH, TBHP, H2O2It is separately added into test tube in sequence, former and later two are one group, are made
A concentration of 100 μM of last solution.Then hydrogen peroxide is added in the row below, the ultimate density for making hydrogen peroxide is 20
μM.Most front-seat first is pure probe, is the solution for only adding in hydrogen peroxide below.It places ten minutes, it then will be all
Solution be put into sepectrophotofluorometer and detect according to sequence from left to right, record data simultaneously preserve.Then again ultraviolet
According to sequence detection from left to right in spectrophotometer, record data and preserve.Test system is pure aquatic system, is contained
HEPES10mM, pH=7.4, CTAB 1mM, recording light spectrogram simultaneously preserve.Test temperature is 25 DEG C.The results are shown in Figure 5.
From fig. 5, it can be seen that when other chaff interferents are added in probe solution, the fluorescent value of solution there is no change
Change, response is not high, but when adding in hydrogen peroxide, solution will be there are one higher response.So probe is to peroxide
Changing hydrogen has relatively good selectivity.Therefore, probe of the invention, which is one, has hydrogen peroxide highly selective probe.
Although with above embodiments describe the present invention, it should be appreciated that before the spirit without departing substantially from the present invention
It puts, the present invention further can be modified and be changed, and these modifications and variation all belong to the scope of protection of the present invention it
It is interior.
Claims (8)
1. compound has following structure
Wherein：R1, R2, R3, R4, R5And R6Independently selected from by hydrogen atom, linear or branched alkyl group, straight or branched alkoxyl,
The group of sulfonic group, ester group and hydroxyl composition；And R therein1, R2, R3, R4, R5And R6It is identical or different.
2. compound according to claim 1, wherein the linear or branched alkyl group, straight or branched alkoxyl are C1-
10 alkyl or alkoxy.
3. compound according to claim 1, wherein the linear or branched alkyl group, straight or branched alkoxyl are C1-5
Alkyl or alkoxy.
4. compound according to claim 1, wherein the linear or branched alkyl group, straight or branched alkoxyl are C1-3
Alkyl or alkoxy.
5. compound according to claim 1, wherein the linear or branched alkyl group is methyl, ethyl, propyl, positive penta
Base, 2- methyl butyls, isobutyl group or 4- methylheptyls.
6. compound according to claim 1, wherein the straight or branched alkoxyl is methoxyl group, ethyoxyl or the third oxygen
Base.
7. compound according to claim 1, wherein：R1, R2, R3, R4, R5And R6Independently selected from hydrogen atom, methyl, second
Base, propyl, methoxyl group, ethyoxyl or propoxyl group.
8. compound according to claim 1 is the compound such as lower structure：
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632441A (en) * | 2016-12-16 | 2017-05-10 | 济南大学 | Ratio type fluorescent probe for identifying hydrogen peroxide |
| CN106749359A (en) * | 2016-11-30 | 2017-05-31 | 中南大学 | A kind of synthesis for detecting hydrogen peroxide novel fluorescence probe and application |
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2018
- 2018-02-23 CN CN201810155915.8A patent/CN108148087A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749359A (en) * | 2016-11-30 | 2017-05-31 | 中南大学 | A kind of synthesis for detecting hydrogen peroxide novel fluorescence probe and application |
| CN106632441A (en) * | 2016-12-16 | 2017-05-10 | 济南大学 | Ratio type fluorescent probe for identifying hydrogen peroxide |
Non-Patent Citations (2)
| Title |
|---|
| FANGYUAN XU, ET AL: "A highly sensitive and photo-stable fluorescent probe for endogenous intracellular H2O2 imaging in live cancer cells", 《DYES AND PIGMENTS》 * |
| YUZHI CHEN, ET AL: "A Fluorescent Probe for Hydrogen Peroxide in Vivo Based on the Modulation of Intramolecular Charge Transfer", 《ANAL. CHEM.》 * |
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