CN105622540A - CO probe and preparation method and application thereof - Google Patents
CO probe and preparation method and application thereof Download PDFInfo
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- CN105622540A CN105622540A CN201510997205.6A CN201510997205A CN105622540A CN 105622540 A CN105622540 A CN 105622540A CN 201510997205 A CN201510997205 A CN 201510997205A CN 105622540 A CN105622540 A CN 105622540A
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- furazan
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- 239000000523 sample Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims abstract description 22
- JKFAIQOWCVVSKC-UHFFFAOYSA-N furazan Chemical compound C=1C=NON=1 JKFAIQOWCVVSKC-UHFFFAOYSA-N 0.000 claims abstract description 21
- CAEWJEXPFKNBQL-UHFFFAOYSA-N prop-2-enyl carbonochloridate Chemical compound ClC(=O)OCC=C CAEWJEXPFKNBQL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 20
- 229910052801 chlorine Inorganic materials 0.000 claims description 20
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims description 20
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 238000004440 column chromatography Methods 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000007850 fluorescent dye Substances 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract description 10
- 238000001514 detection method Methods 0.000 abstract description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- YVWDSXHBXWTADD-UHFFFAOYSA-N 4-nitro-n-propyl-2,1,3-benzoxadiazol-7-amine Chemical compound CCCNC1=CC=C([N+]([O-])=O)C2=NON=C12 YVWDSXHBXWTADD-UHFFFAOYSA-N 0.000 abstract 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 abstract 2
- 239000000047 product Substances 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012141 concentrate Substances 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 238000013016 damping Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/12—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms condensed with carbocyclic rings or ring systems
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- 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
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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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- 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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- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
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- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1048—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with oxygen
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Abstract
The invention belongs to the technical field of detection materials and discloses a CO probe and a preparation method and application thereof. The CO probe has a structural formula shown as the formula (I). According to the preparation method, chloro-paranitrobenzo furazan is added into an n-propylamine organic solution, then anhydrous potassium carbonate is added, the mixture is stirred at room temperature for a reaction, and the reaction product is subjected to separation and purification to obtain 4-propylamino-7-nitro-2,1,3-benzooxadiazole; 4-propylamino-7-nitro-2,1,3-benzo oxadiazole is dissolved in an anhydrous organic solvent, diisopropylethylamine is added under protection of an inert atmosphere, the mixture is stirred and mixed to be uniform, then allyl chloroformate is added dropwise for a reaction at room temperature, and the reaction product is subjected to separation and purification to obtain the CO probe. Through the preparation method, the process is simple, and operation is easy; the obtained CO probe responds to both ultraviolet and fluorescent light and can be applied to the field of CO detection. (Please see the description for the formula (I).).
Description
Technical field
The invention belongs to test material technical field, it is specifically related to a kind of CO probe and its preparation method and application.
Background technology
CO is considered as the killer of a kind of colorless and odorless, after any animal or human sucks high concentration CO, will cause and get killed within the short period of time, and this kind of gas odorlessness, it is difficult to discover in physical environment. The water-gas that modern society uses or liquefied gas, all may cause the leakage of CO, cause the harm of people's lives and properties. But, along with people are to the continuous research of CO, it has been found that also there is important regulating effect function of human body aspect by CO, it is possible to control liver blood circulation, regulates cardiovascular unstriated muscle and the metabolism of self. In order to better control the concentration of CO in the concentration of CO in gas and testing environment, research has high sensitivity, and the method for highly selective monitoring CO concentration has very important significance.
The method of traditional monitoring CO has undispersed infrared method, dynamic coulomb method, penetration type infrared filter method and vapor-phase chromatography etc., and these methods generally exist some defects, such as: instrument price is expensive, complex pretreatment, carries inconvenience etc. In recent years, along with the development of fluorescent probe detection technique, small-molecule fluorescent probe shows distinctive character gradually, numerous advantages such as such as highly sensitive, easy and simple to handle, favorable reproducibility, make organic molecule fluorescent probe day by day become the indispensable research means in the field such as modern life science and medical diagnosis on disease, it is applied to detection and the imaging analysis of target compound in multiple complex biological, environmental sample more and more. Therefore, develop novel be applied to CO detection organic molecule colorimetric and fluorescent probe there is very high using value.
Summary of the invention
In order to solve the shortcoming and defect part of above prior art, the primary and foremost purpose of the present invention is to provide a kind of CO probe.
Another object of the present invention is to provide the preparation method of above-mentioned CO probe.
It is still another object of the present invention to provide the application of above-mentioned CO probe in CO detection field.
The object of the invention is achieved through the following technical solutions:
A kind of CO probe, its chemical structural formula is such as formula shown in (I):
The preparation method of above-mentioned CO probe, comprises following preparation process:
(1) by chlorine, for p-nitrophenyl and furazan joins in Tri N-Propyl Amine organic solution, then adds without aqueous carbonate acid potassium, and stirring at room temperature is reacted, and reaction product, through separation and purification, obtains 4-propylamine base-7-nitro-2,1,3-benzo 4-oxadiazole;
(2) by step (1) gained 4-propylamine base-7-nitro-2; 1; 3-benzo 4-oxadiazole is dissolved in anhydrous organic solvent; add diisopropylethylamine under inert atmosphere protection to be uniformly mixed; then allyl chlorocarbonate it is added dropwise to; room temperature reaction, reaction product, through separation and purification, obtains described CO probe (I).
Preferably, in above-mentioned preparation method, the equivalent of described Tri N-Propyl Amine be chlorine for p-nitrophenyl and the 1��5 of furazan times; Described without aqueous carbonate acid potassium equivalent be chlorine for p-nitrophenyl and the 2��3 of furazan times; The equivalent of described diisopropylethylamine be chlorine for p-nitrophenyl and the 1��5 of furazan times; The equivalent of described allyl chlorocarbonate be chlorine for p-nitrophenyl and the 1��8 of furazan times.
More preferably, the equivalent of described Tri N-Propyl Amine be chlorine for p-nitrophenyl and the 2��3 of furazan times; The equivalent of described diisopropylethylamine be chlorine for p-nitrophenyl and the 2��3 of furazan times; The equivalent of described allyl chlorocarbonate be chlorine for p-nitrophenyl and the 2��4 of furazan times.
Preferably, the anhydrous organic solvent described in Tri N-Propyl Amine organic solution described in step (1) uses organic solvent and step (2) is acetonitrile, tetrahydrofuran (THF), methyl alcohol or ethanol; More preferably acetonitrile or tetrahydrofuran (THF).
Preferably, the separation and purification described in step (1) and step (2) refers to and takes out that filter, filtrate is concentrated and column chromatography purification.
Above-mentioned CO probe is as the application in CO detects of colorimetric probe or fluorescent probe.
The preparation method of the present invention and the product tool obtained have the following advantages and useful effect:
(1) synthesis of probe of the present invention only needs two steps, and last handling process is simple, is easy to operation, and product is easy to get;
(2) probe in detecting 1ppmCO of the present invention can observe the change of color by bore hole, thus quick directly result of determination;
(3) probe of the present invention can realize double-bang firecracker and should detect CO fast, highly sensitive, can observe fluorescence color change under general ultraviolet lamp (365nm); Change based on its specificity and significant color, this probe can be used as the indicator of detection CO fast, also qualitative and quantitative visual colorimetry detection and fluoroscopic examination can be carried out, it is a kind of simple, quick, sensitive, the probe of energy specific detection CO, has broad application prospects in biomolecule detection and environmental area.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of CO probe (I) in embodiment 1;
Fig. 2 is CO probe (I) in embodiment 11HNMR spectrogram;
Fig. 3 is CO probe (I) in embodiment 113CNMR spectrogram;
Fig. 4 is the high resolution mass spectrum figure of CO probe (I) in embodiment 1;
Fig. 5 embodiment 1 gained CO probe (I) in containing palladium ion damping fluid with the uv absorption spectra of CO change in concentration;
Fig. 6 embodiment 1 gained CO probe (I) in containing palladium ion damping fluid with the fluorescence spectrum figure of CO change in concentration.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this. For the parameter not indicated especially, can refer to routine techniques and carry out.
The CORM-3 that following examples use refers to three carbonyl chlorinations (glycine base) ruthenium, is can carry out studying (JamesE.Clark etc., CirculationResearch, 2003 to body as CO; 93:e2-e8).
Core magnetic spectrum adopts Bruker company of Switzerland AvanceIII400MHz nmr determination, and deuterated dimethyl sulfoxide makees solvent; Fluorescence adopts Hitachi, Ltd of Japan F-4500 fluorescence spectrophotometer to measure; Ultraviolet adopts Japan Shimadzu company UV-2450 to measure; High resolution mass spectrum adopts Germany's Agilent 1290/maXisimpact mass spectrograph.
Embodiment 1
(1) by the chlorine of 200mg, for p-nitrophenyl and furazan (1.0mmol) joins in the acetonitrile solution containing 246L Tri N-Propyl Amine (3.0mmol) (15mL), add 300mg Anhydrous potassium carbonate solid, stirring at room temperature reacts 1 hour, taking out filter, filtrate concentrates, column chromatography, obtain 4-propylamine base-7-nitro-2,1,3-benzo 4-oxadiazole (intermediate 1), product rate 64%;
(2) intermediate 1 (0.5mmol) of 111mg is dissolved in 10mL anhydrous acetonitrile; 412 �� L diisopropylethylamine (2.5mmol) stirring at room temperature 0.5 hours afterwards are added under nitrogen protection; then 211 �� L allyl chlorocarbonate (2.0mmol) are slowly added drop-wise in above-mentioned solution; dropwise; room temperature reaction 12 hours, takes out filter, and filtrate concentrates; column chromatography, can obtain CO probe (I) 134mg. Product rate 88%. The synthetic route chart of product is as shown in Figure 1. Product1HNMR spectrogram and13CNMR spectrogram is respectively as shown in Figures 2 and 3; The high resolution mass spectrum figure of product is as shown in Figure 4. Product appraising datum is as follows:
1HNMR(400MHz,d6-DMSO) �� 8.73 (s, 1H), 7.78 (d, J=7.5Hz, 1H), 5.85 (m, 1H), 5.22-5.12 (m, 2H), 4.62 (d, J=5.2Hz, 2H), 3.90 (t, J=7.2Hz, 2H), 1.56 (dd, J=14.6,7.3Hz, 2H), 0.84 (t, J=7.4Hz, 3H);
13CNMR (101MHz, d6-DMSO) �� 153.97,148.40,144.15,137.59,134.34,133.54,132.79,126.63,118.20,67.05,51.94,21.80,11.26;
HR-MS(m/z):307.1034[M+H]+��
Embodiment 2
(1) by the chlorine of 200mg, for p-nitrophenyl and furazan (1.0mmol) joins in the tetrahydrofuran solution containing 247L Tri N-Propyl Amine (15mL), add 280mg Anhydrous potassium carbonate, stirring at room temperature reacts 1 hour, taking out filter, filtrate concentrates, column chromatography, obtain 4-propylamine base-7-nitro-2,1,3-benzo 4-oxadiazole (intermediate 1), product rate 60%;
(2) intermediate 1 (0.5mmol) of 112mg is dissolved in 10mL tetrahydrofuran (THF); 330 �� L diisopropylethylamine (2mmol) stirring at room temperature afterwards are added under nitrogen protection; then 317 �� L allyl chlorocarbonate (3.0mmol) are slowly added drop-wise in above-mentioned solution; dropwise; room temperature reaction spends the night, and takes out filter, and filtrate concentrates; column chromatography, can obtain CO probe (I). Product rate 82%. Product1HNMR spectrogram and13CNMR spectrogram is consistent with Fig. 2 and Fig. 3; High resolution mass spectrum figure and Fig. 4 of product is consistent
Embodiment 3
(1) by 2.0g chlorine, for p-nitrophenyl and furazan joins in the methanol solution containing 2.5mL Tri N-Propyl Amine (120mL), add 2.5g Anhydrous potassium carbonate solid, stirring at room temperature reacts 2 hours, taking out filter, filtrate concentrates, column chromatography, obtain 4-propylamine base-7-nitro-2,1,3-benzo 4-oxadiazole (intermediate 1), product rate 47%;
(2) intermediate 1 of 1.2g is dissolved in 100mL acetonitrile; stirring at room temperature after 3.2mL diisopropylethylamine is added under nitrogen protection; then 2.9mL allyl chlorocarbonate is slowly added drop-wise in above-mentioned solution; dropwise; room temperature reaction spends the night, and takes out filter, and filtrate concentrates; column chromatography, can obtain CO probe (I). Product rate 73%. Product1HNMR spectrogram and13CNMR spectrogram is consistent with Fig. 2 and Fig. 3; High resolution mass spectrum figure and Fig. 4 of product is consistent.
Embodiment 4
(1) by 4.0g chlorine, for p-nitrophenyl and furazan joins in the acetonitrile solution containing 4.8mL Tri N-Propyl Amine (230mL), add 5.9g Anhydrous potassium carbonate solid, stirring at room temperature reacts 2 hours, taking out filter, filtrate concentrates, column chromatography, obtain 4-propylamine base-7-nitro-2,1,3-benzo 4-oxadiazole (intermediate 1), product rate 70%;
(2) intermediate 1 of 2.2g is dissolved in 240mL acetonitrile; stirring at room temperature after 8.2mL diisopropylethylamine is added under nitrogen protection; then 3.0mL allyl chlorocarbonate is slowly added drop-wise in above-mentioned solution; dropwise; room temperature reaction spends the night, and takes out filter, and filtrate concentrates; column chromatography, can obtain CO probe (I). Product rate 85%. Product1HNMR spectrogram and13CNMR spectrogram is consistent with Fig. 2 and Fig. 3; High resolution mass spectrum figure and Fig. 4 of product is consistent.
Gained CO probe performance test of the present invention:
(1) with the ultra-violet absorption spectrum of different concns CO in containing palladium ion damping fluid:
CO probe (I) prepared by Example 1 is dissolved in methyl-sulphoxide, is mixed with 1mM storing solution. Get in the centrifuge tube that storing solution 30 �� L joins 5mL, add the Palladous chloride dimethyl sulfoxide solution of 60 �� L1mM, add the CORM-3 (0-10 equivalent) of different equivalent, then with PBS (10mM, pH=7.40) adjust cumulative volume to 3mL, mix room temperature and place 30min. Adopting ultraviolet spectrophotometer to measure its ultra-violet absorption spectrum, result is as shown in Figure 5. As seen from Figure 5, along with the concentration of CO increases, defining new absorption peak at 480nm, its absorption intensity strengthens along with the amount increase of CO.
(2) with the fluorescence spectrum of different concns CO in containing palladium ion damping fluid:
With the compound method configuration fluorescence liquid to be measured that liquid phase to be measured in above-mentioned (1) is same, adopt the fluorescence spectrum of fluorescent spectrophotometer assay under different concns CO. Result is as shown in Figure 6. As seen from Figure 6, CO probe (I), under 480nm excites, is dispersed at 549nm unstressed configuration, but after adding CO, 549nm place fluorescence intensity significantly increases, and strengthens along with the increase fluorescence intensity of CO concentration.
(3) CO probe (I) Visual retrieval:
Prepare two parts of identical PBS (containing 10 ��Ms of CO probes (I) and 20 ��Ms of Palladous chlorides) with the storing solution in above-mentioned (1), add 0 equivalent and the CORM-3 of 5 equivalents respectively, mix rear incubated at room 30min. There is not any change in the color sample not adding CORM-3, the sample of the CORM-3 adding 5 equivalents turns into yellow from colourless. Under ultraviolet lamp (365nm) irradiates, the sample not adding CORM-3 does not almost have fluorescent emission, and the sample adding the CORM-3 of 5 equivalents sends strong glassy yellow fluorescence. Result shows, CO probe (I) has ultraviolet and fluorescence double-bang firecracker is answered, and can observe color change by bore hole and carry out Analysis for CO.
Above-described embodiment is that the present invention preferably implements mode; but embodiments of the present invention are not restricted to the described embodiments; the change done under the spirit of other any the present invention of not deviating from and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, it is included within protection scope of the present invention.
Claims (8)
1. a CO probe, it is characterised in that, the chemical structural formula of described CO probe is such as formula shown in (I):
2. the preparation method of a kind of CO probe according to claim 1, it is characterised in that comprise following preparation process:
(1) by chlorine, for p-nitrophenyl and furazan joins in Tri N-Propyl Amine organic solution, then adds without aqueous carbonate acid potassium, and stirring at room temperature is reacted, and reaction product, through separation and purification, obtains 4-propylamine base-7-nitro-2,1,3-benzo 4-oxadiazole;
(2) by step (1) gained 4-propylamine base-7-nitro-2; 1; 3-benzo 4-oxadiazole is dissolved in anhydrous organic solvent; add diisopropylethylamine under inert atmosphere protection to be uniformly mixed; then allyl chlorocarbonate it is added dropwise to; room temperature reaction, reaction product, through separation and purification, obtains described CO probe.
3. the preparation method of a kind of CO probe according to claim 2, it is characterised in that: the equivalent of described Tri N-Propyl Amine be chlorine for p-nitrophenyl and the 1��5 of furazan times; Described without aqueous carbonate acid potassium equivalent be chlorine for p-nitrophenyl and the 2��3 of furazan times; The equivalent of described diisopropylethylamine be chlorine for p-nitrophenyl and the 1��5 of furazan times; The equivalent of described allyl chlorocarbonate be chlorine for p-nitrophenyl and the 1��8 of furazan times.
4. the preparation method of a kind of CO probe according to claim 3, it is characterised in that: the equivalent of described Tri N-Propyl Amine be chlorine for p-nitrophenyl and the 2��3 of furazan times; The equivalent of described diisopropylethylamine be chlorine for p-nitrophenyl and the 2��3 of furazan times; The equivalent of described allyl chlorocarbonate be chlorine for p-nitrophenyl and the 2��4 of furazan times.
5. the preparation method of a kind of CO probe according to claim 2, it is characterised in that: the anhydrous organic solvent described in the organic solvent that Tri N-Propyl Amine organic solution described in step (1) uses and step (2) is acetonitrile, tetrahydrofuran (THF), methyl alcohol or ethanol.
6. the preparation method of a kind of CO probe according to claim 5, it is characterised in that: the anhydrous organic solvent described in the organic solvent that Tri N-Propyl Amine organic solution described in step (1) uses and step (2) is acetonitrile or tetrahydrofuran (THF).
7. the preparation method of a kind of CO probe according to claim 2, it is characterised in that: the separation and purification described in step (1) and step (2) refers to takes out that filter, filtrate is concentrated and column chromatography purification.
8. CO probe according to claim 1 is as the application in CO detects of colorimetric probe or fluorescent probe.
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| CN111748003A (en) * | 2020-06-24 | 2020-10-09 | 河北大学 | N-acetamido galactose modified 3-nitrophthalimide derivative, preparation method and application thereof, and liver targeting probe |
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| CN106279059A (en) * | 2016-07-21 | 2017-01-04 | 河南牧业经济学院 | Pd(0 based on 7 nitrobenzofurazan) fluorescent probe and preparation method and application |
| CN108299485A (en) * | 2018-02-09 | 2018-07-20 | 湖北大学 | A kind of fluorescence probe and its preparation method and application for detecting living cells hydrogen peroxide |
| CN108299485B (en) * | 2018-02-09 | 2020-05-12 | 湖北大学 | Fluorescent probe for detecting hydrogen peroxide in living cells and preparation method and application thereof |
| CN108467364A (en) * | 2018-05-30 | 2018-08-31 | 济南大学 | A kind of quick high-selectivity hypersensitive carbon monoxide ratio fluorescence probe |
| CN111748003A (en) * | 2020-06-24 | 2020-10-09 | 河北大学 | N-acetamido galactose modified 3-nitrophthalimide derivative, preparation method and application thereof, and liver targeting probe |
| CN111748003B (en) * | 2020-06-24 | 2021-10-15 | 河北大学 | N-acetamido galactose modified 3-nitrophthalimide derivative, preparation method and application thereof, and liver targeting probe |
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