CN108148013A - A kind of zinc ion probe and preparation method and application - Google Patents
A kind of zinc ion probe and preparation method and application Download PDFInfo
- Publication number
- CN108148013A CN108148013A CN201810093797.2A CN201810093797A CN108148013A CN 108148013 A CN108148013 A CN 108148013A CN 201810093797 A CN201810093797 A CN 201810093797A CN 108148013 A CN108148013 A CN 108148013A
- Authority
- CN
- China
- Prior art keywords
- zinc ion
- preparation
- ion probe
- solution
- step reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000523 sample Substances 0.000 title claims abstract description 46
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 238000001514 detection method Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000007857 hydrazones Chemical class 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 4
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 45
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 27
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000011701 zinc Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000007832 Na2SO4 Substances 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- QQEDYUHGZYMULN-UHFFFAOYSA-N 10h-phenoxazin-3-amine Chemical compound C1=CC=C2OC3=CC(N)=CC=C3NC2=C1 QQEDYUHGZYMULN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- DXRFZHILMCWCNG-UHFFFAOYSA-N N,N-dimethyl-1,8-naphthyridin-2-amine Chemical compound C1=CC=NC2=NC(N(C)C)=CC=C21 DXRFZHILMCWCNG-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 206010060862 Prostate cancer Diseases 0.000 description 1
- 208000000236 Prostatic Neoplasms Diseases 0.000 description 1
- 240000000203 Salix gracilistyla Species 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- -1 aldehyde hydrazone Chemical class 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 230000006907 apoptotic process Effects 0.000 description 1
- 230000004596 appetite loss Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 208000033065 inborn errors of immunity Diseases 0.000 description 1
- 235000021266 loss of appetite Nutrition 0.000 description 1
- 208000019017 loss of appetite Diseases 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 208000028529 primary immunodeficiency disease Diseases 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000022983 regulation of cell cycle Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
- C07D265/38—[b, e]-condensed with two six-membered rings
-
- 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
- G01N21/17—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
-
- 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
-
- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—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
- 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
-
- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
Abstract
The invention discloses a kind of zinc ion probe and synthetic method and applications, belong to analysis detection field.This method is reacted with chloracetyl chloride under the action of alkalescent catalyst using chemical compounds I as raw material, obtains compound ii；Under the conditions of alkalescent salt, compound ii is reacted with salicylide hydrazone, obtains compound III.Synthetic method of the present invention is simple, is easy to industrialized production, and high selectivity low as probe molecule detection zinc ion detection limit.
Description
Technical field
The invention belongs to analyze detection field, and in particular to a kind of zinc ion probe and synthetic method and application.
Background technology
Zinc ion is a kind of essential trace element in organism, is widely existed in cell and body fluid, in life
In the physiology courses such as long development, reproduction, nerve signal transmission, gene typing, nucleic acid recognizing, cell cycle regulation, apoptosis zinc from
Son plays an important roll.The intake of zinc ion is excessive or deficiency can all make the growth and development of organism disorderly, causes a variety of diseases
Disease, such as loss of appetite, hypoimmunity, diabetes, prostate cancer disease are all unbalance related with zinc ion.Therefore, exploitation and
It studies novel zinc ion detection method and important meaning is suffered from for bioscience and environmental science.
Invention content
The present invention be directed to the shortcomings of the prior art to provide a kind of zinc ion probe and synthetic method and application.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of zinc ion probe, the structural formula of the probe are as follows：
。
A kind of preparation method of above-mentioned zinc ion probe, reaction route are as follows：
。
Specifically include following steps：
The first step：This method carries out instead using chemical compounds I as raw material under the action of alkalescent catalyst with chloracetyl chloride
Should, obtain compound ii；
In some embodiment schemes：First step reaction solvent used is dichloromethane, tetrahydrofuran, toluene.First
Step reaction alkalescent catalyst used is any one in dimethylamino naphthyridine, pyridine and triethylamine.First step reaction temperature
Spend is -10~0 DEG C.
In some more specifically embodiment：The molar ratio of chemical compounds I and alkalescent catalyst is 1:1-1:5.
Second step：It is catalyst in potassium iodide, under the conditions of existing for acid binding agent, compound ii carries out anti-with salicylide hydrazone
Should, obtain compound III.
In some embodiment schemes：Second step reaction solvent used is acetonitrile, ethyl alcohol, dichloromethane.Second step is anti-
Acid binding agent that should be used is at least one of potassium carbonate, sodium carbonate and triethylamine.Second step reaction temperature is is heated to reflux temperature
Degree.
In some more specifically embodiment：The molar ratio of compound ii and acid binding agent is 1:1-1:10.
In technical solution of the present invention：Application of the above-mentioned probe as detection zinc ion.
Beneficial effects of the present invention：
Synthetic method of the present invention is simple, is easy to industrialized production, and choosing low as probe molecule detection zinc ion detection limit
Selecting property height.
Description of the drawings
Fig. 1 is probe molecule hhpa to Zn2+Selective absorbing spectral matching factor.
Fig. 2 is Zn2+Figure is titrated to the absorption spectrum of probe molecule hhpa.
Fig. 3 is probe molecule hhpa to Zn2+Selective fluorescence spectrum identification.
Fig. 4 is Zn2+To the fluorescence spectroscopic titration figure of probe molecule hhpa.
Fig. 5 is to probe hhpa Selective recognitions Zn when there is other coexistent metallic ions in solution2+Influence figure.
Fig. 6 is Zn2+With influence figure fluorescence intensity of the probe molecule hhpa reaction time to solution fluorescence intensity.
Fig. 7 is probe molecule hhpa in different Zn2+Fluorescence intensity in strength solution.
Specific embodiment
With reference to embodiment, the present invention will be further described, and but the scope of the present invention is not limited thereto：
Embodiment 1
Phenoxazine -3- amine (1.98g, 10mmol), 100mL dichloromethane and 4- are sequentially added in 250mL three-neck flasks
Dimethylamino naphthyridine (1.22g, 10mmol), is fully cooled in ice salt bath, then with constant pressure funnel by 20mL dissolved with chloroethene
The dichloromethane solution of acyl chlorides (1.13g, 10mmol) is slowly added drop-wise in the three-neck flask being sufficiently stirred, and controls three-neck flask
In reacting liquid temperature do not exceed 0 DEG C, after being added dropwise to complete, continue to react 2h in ice salt bath.After the completion of reaction, use
The NaOH solution of 0.1mol/L adjusts the pH value of reaction solution to 9 or so.Then reaction solution is extracted with dichloromethane (3 × 25mL),
Merge organic phase and washed, then use anhydrous Na with water (3 × 25mL)2SO4It is dried overnight.Filtrate is rotated after filtering, is removed organic molten
Agent obtains II 2.54g of blue-green solid product, yield：92.7%, purity：99.36%.Elemental analysis：(%) for
C14H11N2O2Cl:Calculated value：C 61.21；H 4.04；N 10.20, measured value：C 61.43；H 4.18；N 10.07.
IR(KBr),ν,cm-1:3462,3397,1638,1329,1287,1209,1117,1083,921,848,741,
718。
1H NMR(500MHz,CDCl3,TMS):δ=7.73 (s, 1H), 7.45 (s, 1H), 7.24 (d, J=7.2,1H),
6.83 (t, J=7.2,1H), 6.72-6.68 (m, 2H), 6.61-6.57 (m, 2H), 6.42 (s, 1H), 4.31 (s, 2H) ppm.
In the flask of 100mL, by compound ii (1.37g, 5mmol), potassium iodide (0.83mg, 0.005mmol) and nothing
Aqueous carbonate potassium (1.38g, 5mmol) is dissolved in the acetonitrile of 40mL, under conditions of reflux and stirring, is slowly added dropwise with constant pressure funnel
Dissolved with the acetonitrile solution of the 15mL of salicylide hydrazone (0.68g, 5mmol), control and dripped off in 1h.Continue back flow reaction after being added dropwise to complete
Reaction solution is cooled to room temperature by 20h after reaction, and reaction solution is poured into water.Then extracted with dichloromethane (3 × 25mL)
It takes, merges organic phase, then washed with saturation NaCl solution (3 × 25mL).Organic phase anhydrous Na2SO4It is dried overnight.After filtering
Filtrate is rotated, organic solvent is removed, obtains crude product.This crude product is crossed into silicagel column purification (ethyl acetate：Petroleum ether=1:
5), solvent evaporated obtains blue-green solid product III (hhpa) 1.72g, yield：92.0%, purity：99.43%.
Elemental analysis：(%) for C21H18N4O3:Calculated value：C 67.37；H 4.85；N 14.96, measured value：C
67.51；H 4.83； N 14.78.
IR(KBr),ν,cm-1:3413,1624,1406,1338,1276,1251,1210,1127,1064,961,917,
854,731,662,618。 1H NMR(500MHz,CDCl3,TMS):10.23 (s, 1H), 8.61 (s, 1H), 8.41 (t, J=
7.2,1H), 7.71 (s, 1H), 7.43 (s, 1H), 7.41-7.35 (m, 2H), 7.23-7.19 (m, 3H), 6.85 (t, J=7.2,
1H), 6.72-6.67 (m, 2H), 6.62-6.57 (m, 2H), 6.42 (s, 1H), 4.25 (d, J=7.2,2H) ppm.
Embodiment 2
Sequentially added in 250mL three-neck flasks phenoxazine -3- amine (1.98g, 10mmol), 100mL tetrahydrofurans and
3mL pyridines, are fully cooled in ice salt bath, then with constant pressure funnel by 20mL dissolved with chloracetyl chloride (1.13g, 10mmol)
Dichloromethane solution be slowly added drop-wise in the three-neck flask being sufficiently stirred, control three-neck flask in reacting liquid temperature should not
More than 0 DEG C, after being added dropwise to complete, continue to react 2h in ice salt bath.After the completion of reaction, with the NaOH solution tune of 0.1mol/L
The pH value of reaction solution is saved to 9 or so.Then with dichloromethane (3 × 25mL) extract reaction solution, merge organic phase and with water (3 ×
It 25mL) washes, then uses anhydrous Na2SO4It is dried overnight.Filtrate is rotated after filtering, removes organic solvent, obtains blue-green solid production
II 2.50g of object, yield：91.2%, purity：99.27%.
In the flask of 100mL, by compound ii (1.37g, 5mmol), potassium iodide (0.83mg, 0.005mmol) and nothing
Aqueous sodium carbonate (2.12g, 10mmol) is dissolved in the ethyl alcohol of 40mL, under conditions of reflux and stirring, is slowly dripped with constant pressure funnel
Solubilization has the acetonitrile solution of the 15mL of salicylide hydrazone (0.68g, 5mmol), controls and is dripped off in 1h.It is anti-to continue reflux after being added dropwise to complete
20h is answered, is after reaction cooled to room temperature reaction solution, and reaction solution is poured into water.Then dichloromethane (3 × 25mL) is used
Extraction merges organic phase, then is washed with saturation NaCl solution (3 × 25mL).Organic phase anhydrous Na2SO4It is dried overnight.Filtering
Filtrate is rotated afterwards, organic solvent is removed, obtains crude product.This crude product is crossed into silicagel column purification (ethyl acetate：Petroleum ether=
1:5), solvent evaporated obtains blue-green solid product III (hhpa) 1.69g, yield：90.4%, purity：99.31%.
Embodiment 3
Phenoxazine -3- amine (1.98g, 10mmol), 100mL toluene and 7mL tri- are sequentially added in 250mL three-neck flasks
Ethamine is fully cooled in ice salt bath, then with constant pressure funnel by 20mL dissolved with the two of chloracetyl chloride (1.13g, 10mmol)
Chloromethanes solution is slowly added drop-wise in the three-neck flask being sufficiently stirred, and the reacting liquid temperature in three-neck flask is controlled not exceed
0 DEG C, after being added dropwise to complete, continue to react 2h in ice salt bath.After the completion of reaction, adjusted with the NaOH solution of 0.1mol/L anti-
The pH value of liquid is answered to 9 or so.Then reaction solution is extracted with dichloromethane (3 × 25mL), merges organic phase and with water (3 × 25mL)
It washes, then uses anhydrous Na2SO4It is dried overnight.Filtrate is rotated after filtering, organic solvent is removed, obtains blue-green solid product II
2.46g yield：89.8%, purity：98.77%.
In the flask of 100mL, by compound ii (1.37g, 5mmol), potassium iodide (0.83mg, 0.005mmol) and
7mL triethylamines are dissolved in the dichloromethane of 40mL, under conditions of reflux and stirring, are slowly added dropwise with constant pressure funnel dissolved with bigcatkin willow
The acetonitrile solution of the 15mL of aldehyde hydrazone (0.68g, 5mmol), controls and is dripped off in 1h.Continue back flow reaction 20h, reaction after being added dropwise to complete
After reaction solution is cooled to room temperature, and reaction solution is poured into water.Then it is extracted, merged with dichloromethane (3 × 25mL)
Organic phase, then washed with saturation NaCl solution (3 × 25mL).Organic phase anhydrous Na2SO4It is dried overnight.By filtrate after filtering
Revolving removes organic solvent, obtains crude product.This crude product is crossed into silicagel column purification (ethyl acetate：Petroleum ether=1:5) it, steams
Dry solvent obtains blue-green solid product III (hhpa) 1.63g, yield：87.2%, purity：99.27%.
Property section
1st, absorption spectrum is tested
Probe molecule hhpa is to Zn2+Absorption spectrum identification
As shown in Figure 1, it is a concentration of to be separately added into 10 μ L in a concentration of 0.1mmol/L probe molecules hhpa solution of 10mL
Metal ion solution (the Ag of 0.5mol/L (5 times of moles)+、Na+、K+、Ca2+、Cd2+、Mn2+、Mg2+、Co2+、 Cu2+、Ni2+、
Pb2+、Hg2+、Al3+、Zn2+).Solution system used in experiment is the mixed solution of acetonitrile/water (v/v=1/2), is absorbed
Spectrum measures on Shimadzu UV-2450 type ultraviolet specrophotometers.Probe molecule is in acetonitrile/water (v/v=as seen from Figure 1
1/2) absorption of itself is in 580nm or so in mixed solution, when we added in into probe molecule solutions excessive metal from
After son, it has been found that only adding in Zn2+Afterwards, originally it is located at the absorption peak at 580nm to disappear, and there are one new at 460nm
New absorption peak occur, blue shift 120nm, the color of solution also become yellow from blue, and when in probe molecule solutions
When adding in other metal ions, then without the generation of this phenomenon, this illustrates the absorption spectrum of the probe molecule to Zn2+Have solely
Special response.
As shown in Fig. 2, sequentially add 0.05 in a concentration of 0.1mmol/L probes hhpa solution of 10mL, 0.1,0.15,
0.2、0.25、0.3、0.35、0.4、0.45、0.5、0.55、0.6、0.65、0.7、0.75、0.8、0.85、0.9、0.95、 1.0、
1.2nd, the Zn of 1.5 times of moles2+.Solution system used in experiment is the mixed solution of acetonitrile/water (v/v=1/2), is inhaled
Spectrum is received to measure on Shimadzu UV-2450 type ultraviolet specrophotometers.As seen from Figure 2, with Zn2+Addition, solution
Absorbing wavelength is gradually blue shifted to 460nm by 580nm, works as Zn2+After addition reaches 1 times of mole of probe molecule, the suction of solution
Wavelength is received no longer to move, and the intensity of absorption peak is held essentially constant.This illustrates probe molecule hhpa and Zn2+It is 1:1 coordination
's.
2nd, fluorescence spectrum experiments
Probe molecule hhpa is to Zn2+Fluorescence identifying
As shown in figure 3, probe molecule ddpb is dissolved in the mixed solution of acetonitrile/water (v/v=1/2), it is configured to concentration
For the solution of 10 μm of ol/L, it is separately added into the metal ion (Ag of 5 times of moles in this solution+、Na+、K+、Ca2+、 Cd2+、Mn2 +、Mg2+、Co2+、Cu2+、Ni2+、Pb2+、Hg2+、Al3+、Zn2+).Excitation wavelength is 460nm, measures the fluorescence spectrum of solution.From Fig. 3
In as can be seen that probe molecule solutions 665nm at there are one compared with hypofluorescence emission peak, in the Zn for adding in excess2+Afterwards, solution exists
At 665nm hypofluorescence emission peak disappear, and 585nm at appearance one very strong fluorescence emission peak, and add in other metals from
It is sub then without this phenomenon, this illustrates the probe molecule to Zn2+Show very strong fluorescence selection identity.Made in experiment
Solution system is the mixed solution of acetonitrile/water (v/v=1/2), and fluorescence spectrum is in AMINCO Bowman Series 2
It is measured in Fluorescence Spectrometer.
As shown in figure 4, in the mixed solution of the acetonitrile/water (v/v=1/2) of the probe molecule hhpa of 10 μm of ol/L, point
Not Jia Ru 0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,
0.8th, the Zn of 0.85,0.9,0.95,1.0,1.2,1.5 times of mole2+.It is excited at 460nm, measures the emission spectrum of solution,
As depicted with Zn2+Concentration increase, 665nm places hypofluorescence emission peak gradually weaken it is final disappear, and the appearance at 585nm
One new fluorescence emission peak, and in Zn2+Addition reaches emission peak intensity after 1 times of mole at 585nm substantially not
It is further added by.
As shown in figure 5, in the mixed solution of the acetonitrile/water (v/v=1/2) of the probe molecule hhpa of 10 μm of ol/L, point
Metal ion (the Ag dissolved with 10 times of moles is not added in+、Na+、K+、Ca2+、Cd2+、Mn2+、Mg2+、Co2+、 Cu2+、Ni2+、Pb2+、
Hg2+、Al3+), at excitation wavelength 460nm, launch wavelength 585nm, the fluorescence intensity of solution is measured, then again in above-mentioned solution
The middle Zn for adding in 10 times of moles2+, at excitation wavelength 460nm, launch wavelength 585nm, the fluorescence intensity of solution is measured, from
In Fig. 5 as can be seen that when, largely there are during other metal ions, probe molecule hhpa is to Zn in solution2+Selective recognition simultaneously
It is unaffected.
As shown in fig. 6, in the mixed solution of the acetonitrile/water (v/v=1/2) of the probe molecule hhpa of 10 μm of ol/L, add
Enter the Zn of 2 times of moles2+.At excitation wavelength 460nm, launch wavelength 585nm, respectively 0,1,2,3,4,5,6,7,8,9,10
The fluorescence intensity of recording solution during minute.As shown in fig. 6, add in Zn in probe molecule hhpa solution2+After 2 minutes, fluorescence hair
It penetrates intensity and reaches maximum value, and be held essentially constant as time went on.
As shown in fig. 7, respectively in the Zn of a concentration of 0.2-2 μm of ol/L of 10mL (with 0.05 μm of ol/L increasing concen-trations)2+Acetonitrile/
The hhpa solution of a concentration of 1mmol/L of 0.1mL is added in the mixed solution of water (v/v=1/2), in excitation wavelength 460nm, transmitting
At wavelength 585nm, the fluorescence intensity of solution is measured.As can be seen from the figure work as Zn2+Concentration is in the range of 0.2-1.1 μm of ol/L
Good linear relationship (R2=0.9988) is showed, 1.26 × 10 are limited to using the detection obtained by 3 σ IUPAC criterion calculations- 7mol/L。
Claims (10)
1. a kind of zinc ion probe, it is characterised in that：
。
2. a kind of preparation method of zinc ion probe described in claim 1, it is characterised in that：
。
3. a kind of preparation method of the zinc ion probe described in claim 2, it is characterised in that：This method includes the following steps：
The first step：This method is reacted with chloracetyl chloride under the action of alkalescent catalyst, is obtained using chemical compounds I as raw material
To compound ii；
Second step：Using potassium iodide as catalyst, under the conditions of existing for acid binding agent, compound ii is reacted with salicylide hydrazone,
Obtain compound III.
4. the preparation method of zinc ion probe according to claim 3, it is characterised in that：First step reaction solvent used
For dichloromethane, tetrahydrofuran, toluene.
5. the preparation method of zinc ion probe according to claim 3, it is characterised in that：First step reaction weak base used
Property catalyst be any one in 4-dimethylaminopyridine, pyridine and triethylamine.
6. the preparation method of zinc ion probe according to claim 3, it is characterised in that：First step reaction temperature is -10
~0 DEG C.
7. the preparation method of zinc ion probe according to claim 3, it is characterised in that：Second step reaction solvent used
For acetonitrile, ethyl alcohol, dichloromethane.
8. the preparation method of zinc ion probe according to claim 3, it is characterised in that：Acid is tied up used in second step reaction
Agent is at least one of potassium carbonate, sodium carbonate and triethylamine.
9. the preparation method of zinc ion probe according to claim 3, it is characterised in that：Second step reaction temperature is heating
Reflux temperature.
10. application of the probe described in claim 1 as detection zinc ion.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810919392.XA CN108863975B (en) | 2018-01-31 | 2018-01-31 | A kind of preparation method of zinc ion probe |
| CN201810093797.2A CN108148013B (en) | 2018-01-31 | 2018-01-31 | A kind of zinc ion probe and preparation method and application |
| CN201810948737.4A CN108997249B (en) | 2018-01-31 | 2018-01-31 | Application of probe |
| CN201810908578.5A CN108863974B (en) | 2018-01-31 | 2018-01-31 | Probe for detecting zinc ions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810093797.2A CN108148013B (en) | 2018-01-31 | 2018-01-31 | A kind of zinc ion probe and preparation method and application |
Related Child Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810948737.4A Division CN108997249B (en) | 2018-01-31 | 2018-01-31 | Application of probe |
| CN201810908578.5A Division CN108863974B (en) | 2018-01-31 | 2018-01-31 | Probe for detecting zinc ions |
| CN201810919392.XA Division CN108863975B (en) | 2018-01-31 | 2018-01-31 | A kind of preparation method of zinc ion probe |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108148013A true CN108148013A (en) | 2018-06-12 |
| CN108148013B CN108148013B (en) | 2018-10-23 |
Family
ID=62459478
Family Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810919392.XA Expired - Fee Related CN108863975B (en) | 2018-01-31 | 2018-01-31 | A kind of preparation method of zinc ion probe |
| CN201810908578.5A Expired - Fee Related CN108863974B (en) | 2018-01-31 | 2018-01-31 | Probe for detecting zinc ions |
| CN201810948737.4A Expired - Fee Related CN108997249B (en) | 2018-01-31 | 2018-01-31 | Application of probe |
| CN201810093797.2A Expired - Fee Related CN108148013B (en) | 2018-01-31 | 2018-01-31 | A kind of zinc ion probe and preparation method and application |
Family Applications Before (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810919392.XA Expired - Fee Related CN108863975B (en) | 2018-01-31 | 2018-01-31 | A kind of preparation method of zinc ion probe |
| CN201810908578.5A Expired - Fee Related CN108863974B (en) | 2018-01-31 | 2018-01-31 | Probe for detecting zinc ions |
| CN201810948737.4A Expired - Fee Related CN108997249B (en) | 2018-01-31 | 2018-01-31 | Application of probe |
Country Status (1)
| Country | Link |
|---|---|
| CN (4) | CN108863975B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108863974A (en) * | 2018-01-31 | 2018-11-23 | 南京晓庄学院 | It is a kind of for detecting the probe of zinc ion |
| CN111718276A (en) * | 2019-12-20 | 2020-09-29 | 南京晓庄学院 | Synthesis method of derivative |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820811A (en) * | 2016-04-28 | 2016-08-03 | 南京晓庄学院 | Fluorescent probe, and synthesis method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107860732B (en) * | 2017-04-19 | 2019-05-24 | 南京晓庄学院 | A kind of purposes of multi signal probe |
| CN108863975B (en) * | 2018-01-31 | 2019-05-21 | 南京晓庄学院 | A kind of preparation method of zinc ion probe |
-
2018
- 2018-01-31 CN CN201810919392.XA patent/CN108863975B/en not_active Expired - Fee Related
- 2018-01-31 CN CN201810908578.5A patent/CN108863974B/en not_active Expired - Fee Related
- 2018-01-31 CN CN201810948737.4A patent/CN108997249B/en not_active Expired - Fee Related
- 2018-01-31 CN CN201810093797.2A patent/CN108148013B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820811A (en) * | 2016-04-28 | 2016-08-03 | 南京晓庄学院 | Fluorescent probe, and synthesis method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| M.M.EL-KERDAWY ET AL.: "Synthesis of New 10-Substituted Phenothiazine Derivatives", 《JOURNAL F.PRAKT.CHEMIE》 * |
| YADAV, R.ET AL: "Synthesis of 2-Aryl-3-N10-[(acetylamino)-1,3-thiazolidin-4-ones] (VIII) and 5-Arylidine-2-aryl-3-N10-[(acetylamino)-1,3-thiazolidin-4-ones] (IX) and Their Antimicrobial and Diuretic Activities", 《CHEMINFORM》 * |
| 王秀丽等: "酸性条件下不同含氮取代基对吩噁嗪PET 效应的比较研究", 《中国化学会第30届学术年会》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108863974A (en) * | 2018-01-31 | 2018-11-23 | 南京晓庄学院 | It is a kind of for detecting the probe of zinc ion |
| CN108997249A (en) * | 2018-01-31 | 2018-12-14 | 南京晓庄学院 | A kind of purposes of probe |
| CN111718276A (en) * | 2019-12-20 | 2020-09-29 | 南京晓庄学院 | Synthesis method of derivative |
| CN111718276B (en) * | 2019-12-20 | 2021-03-30 | 南京晓庄学院 | Synthesis method of derivative |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108148013B (en) | 2018-10-23 |
| CN108997249B (en) | 2020-07-17 |
| CN108863974B (en) | 2020-07-17 |
| CN108863975B (en) | 2019-05-21 |
| CN108997249A (en) | 2018-12-14 |
| CN108863975A (en) | 2018-11-23 |
| CN108863974A (en) | 2018-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108148013B (en) | A kind of zinc ion probe and preparation method and application | |
| CN104962278B (en) | Palladium ion fluorescent probe, and preparation method and applications thereof | |
| CN109467551B (en) | Preparation process of coumarin fluorescent probe molecule for selectively detecting GSH | |
| CN105541876A (en) | Anthraquinone-bridged N-heterocyclic carbene metal complex and preparation method and application thereof | |
| CN114702475B (en) | Synthesis process of nicotine with single configuration | |
| CN104478823B (en) | The benzofuraxan compound of polylysine modification and synthetic method, application, recovery method and the method for detection copper ion concentration | |
| CN105820811B (en) | A kind of fluorescence probe and synthetic method and its application | |
| CN108164448B (en) | A kind of anthraquinone derivative and synthetic method and application | |
| CN113999218B (en) | Flavonol compound, preparation method and application thereof in detection of biological mercaptan | |
| CN105294540A (en) | Novel Schiff base compound taking triphenylamine as center and preparation of novel Schiff base compound | |
| CN110922338B (en) | Anthraquinone derivative and synthesis method and application thereof | |
| CN110041308A (en) | A kind of high symmetry sandwich structure imines Zn complex | |
| CN108912096A (en) | A kind of leptospira structure imines iron complex | |
| Ibrahim et al. | Evaluation of antitumor activity of copper complexes of coumarin in breast and lung cancer | |
| CN115785129B (en) | Spiropyrano copper complex and preparation method and application thereof | |
| CN110590784A (en) | Derivative based on pyrrolopyrroledione and preparation method and application thereof | |
| CN107353308B (en) | Two thiophene phenol ethylene complex of iridium of phosphorescence conversion behavior and preparation method thereof with soda acid induction | |
| CN113637027B (en) | Phenyl triazole dicarboxylic acid-rhodamine B derivative fluorescent probe and preparation method and application thereof | |
| CN107827844A (en) | A kind of method for synthesizing butyrolactone derivative | |
| CN110563702B (en) | Near-infrared fluorescent compound, preparation method and application thereof in detecting ferrous ions | |
| CN114907376B (en) | Molecular machine based on bi-m-benzene-32-crown-10 main body cave ether and preparation method thereof | |
| CN108218880A (en) | A kind of novel mercury ion optical probe and preparation method and application | |
| RU2620270C1 (en) | Tetra-4-[4-(1-methyl-1-phenylethyl)phenoxy]tetra-5-nitrophthalocyanines cobalt and nickel | |
| CN104926843A (en) | Azacyclocarbene trinuclear metallic silver complex and preparation method and application thereof | |
| CN117800962A (en) | Method for synthesizing cinchona alkaloid dimer catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181023 Termination date: 20220131 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |