CN108863975B - A kind of preparation method of zinc ion probe - Google Patents
A kind of preparation method of zinc ion probe Download PDFInfo
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- CN108863975B CN108863975B CN201810919392.XA CN201810919392A CN108863975B CN 108863975 B CN108863975 B CN 108863975B CN 201810919392 A CN201810919392 A CN 201810919392A CN 108863975 B CN108863975 B CN 108863975B
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- zinc ion
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- ion probe
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- 239000000523 sample Substances 0.000 title claims abstract description 42
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 150000007857 hydrazones Chemical class 0.000 claims abstract description 6
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- 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 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 15
- 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000002253 acid Substances 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
- 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 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
- 238000001514 detection method Methods 0.000 abstract description 9
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 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
- 239000011701 zinc Substances 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000007832 Na2SO4 Substances 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
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 230000005284 excitation Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003960 organic solvent 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
- 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
- 238000010586 diagram Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 206010012559 Developmental delay Diseases 0.000 description 1
- 206010060862 Prostate cancer Diseases 0.000 description 1
- 208000000236 Prostatic Neoplasms Diseases 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
- 150000001412 amines Chemical class 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
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 208000037824 growth disorder Diseases 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 239000012071 phase Substances 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
- 230000035484 reaction time Effects 0.000 description 1
- 230000022983 regulation of cell cycle Effects 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
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- 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
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- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- 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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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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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
- 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
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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
- C09K2211/1029—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
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Abstract
The invention discloses a kind of preparation methods of zinc ion probe, 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, easy to industrialized production, and selectivity height low as probe molecule detection zinc ion detection limit.
Description
The application is the applying date are as follows: 2018-01-31, application No. is a kind of 2018100937972, titles are as follows: zinc ion
The divisional application of the patent of invention of probe and preparation method and application.
Technical field
The invention belongs to analysis detection fields, and in particular to a kind of preparation method of zinc ion probe.
Background technique
Zinc ion is a kind of essential microelement in organism, is widely existed in cell and body fluid, in life
In the physiology courses such as long development, reproduction, nerve signal transmitting, gene typing, nucleic acid recognizing, cell cycle regulation, apoptosis zinc from
Son plays a significant role.The intake of zinc ion is excessive or the insufficient growth and development disorder that can all make organism, 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 suffers from important meaning for bioscience and environmental science.
Summary of the invention
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 includes the following steps:
Step 1: this method using chemical compounds I as raw material, carries out anti-under the action of alkalescent catalyst with chloracetyl chloride
It answers, obtains compound ii;
In some example schemes: first step reaction solvent used is methylene chloride, tetrahydrofuran, toluene.First
Step reaction alkalescent catalyst used is any one in dimethylamino naphthyridine, pyridine and triethylamine.First step reaction temperature
Degree is -10~0 DEG C.
In some more specifically embodiments: the molar ratio of chemical compounds I and alkalescent catalyst is 1:1-1:5.
Step 2: be catalyst in potassium iodide, under the conditions of existing for the acid binding agent, compound ii and salicylide hydrazone carry out anti-
It answers, obtains compound III.
In some example schemes: second step reaction solvent used is acetonitrile, ethyl alcohol, methylene chloride.Second step is anti-
Answering acid binding agent used is at least one of potassium carbonate, sodium carbonate and triethylamine.Second step reaction temperature is to be heated to reflux temperature
Degree.
In some more specifically embodiments: 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 in detection zinc ion.
Beneficial effects of the present invention:
Synthetic method of the present invention is simple, easy to industrialized production, and choosing low as probe molecule detection zinc ion detection limit
Selecting property height.
Detailed description of the invention
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 when there is other coexistent metallic ions in solution to probe hhpa Selective recognition Zn2+Influence diagram.
Fig. 6 is Zn2+With the probe molecule hhpa reaction time to the influence diagram of solution fluorescence intensity.
Fig. 7 is probe molecule hhpa in different Zn2+Fluorescence intensity in strength solution.
Specific embodiment
Below 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 methylene chloride and 4- are sequentially added in 250mL three-neck flask
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, 2h is reacted in continuation in ice salt bath.After the reaction was completed, it uses
The NaOH solution of 0.1mol/L adjusts the pH value of reaction solution to 9 or so.Then reaction solution is extracted with methylene chloride (3 × 25mL),
Merge organic phase and washed with water (3 × 25mL), then uses anhydrous Na2SO4It 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;H4.18;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 is 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 methylene chloride (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.By this crude product cross 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
Phenoxazine -3- amine (1.98g, 10mmol), 100mL tetrahydrofuran and 3mL are sequentially added in 250mL three-neck flask
Pyridine 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 controlled in three-neck flask does not exceed
0 DEG C, after being added dropwise to complete, 2h is reacted in continuation in ice salt bath.After the reaction was completed, reaction is adjusted with the NaOH solution of 0.1mol/L
The pH value of liquid is to 9 or so.Then reaction solution is extracted with methylene chloride (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
2.50g, 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), and control 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 methylene chloride (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.By this crude product cross 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
Tri- second of phenoxazine -3- amine (1.98g, 10mmol), 100mL toluene and 7mL is sequentially added in 250mL three-neck flask
Amine is fully cooled in ice salt bath, then with constant pressure funnel by 20mL dissolved with the dichloro of chloracetyl chloride (1.13g, 10mmol)
Dichloromethane is slowly added drop-wise in the three-neck flask being sufficiently stirred, and the reacting liquid temperature controlled in three-neck flask does not exceed 0
DEG C, after being added dropwise to complete, 2h is reacted in continuation in ice salt bath.After the reaction was completed, reaction is adjusted with the NaOH solution of 0.1mol/L
The pH value of liquid is to 9 or so.Then reaction solution is extracted with methylene chloride (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
Triethylamine is dissolved in the methylene chloride of 40mL, under conditions of reflux and stirring, is slowly added dropwise with constant pressure funnel dissolved with salicylide
The acetonitrile solution of the 15mL of hydrazone (0.68g, 5mmol), control are dripped off in 1h.Continue back flow reaction 20h, reaction knot after being added dropwise to complete
Reaction solution is cooled to room temperature after beam, and reaction solution is poured into water.Then it is extracted, is associated with methylene chloride (3 × 25mL)
Machine phase, then washed with saturation NaCl solution (3 × 25mL).Organic phase anhydrous Na2SO4It is dried overnight.Filtrate is revolved after filtering
It steams, removes organic solvent, obtain crude product.This crude product is crossed into silicagel column purification (ethyl acetate: petroleum ether=1:5), is evaporated
Solvent obtains blue-green solid product III (hhpa) 1.63g, yield: 87.2%, purity: 99.27%.
Property section
1, absorption spectrum is tested
Probe molecule hhpa is to Zn2+Absorption spectrum identification
As shown in Figure 1, being to be separately added into 10 μ L concentration in 0.1mmol/L probe molecule hhpa solution to be in 10mL concentration
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), absorbs light
Spectrum measures on Shimadzu UV-2450 type ultraviolet specrophotometer.Probe molecule is in acetonitrile/water (v/v=1/ as seen from Figure 1
2) absorption of itself is in 580nm or so in mixed solution, when excessive metal ion is added into probe molecule solutions for we
Afterwards, it has been found that Zn only is being added2+Afterwards, originally be located at 580nm place absorption peak disappear, and have at 460nm one newly
New absorption peak occurs, blue shift 120nm, and the color of solution also becomes yellow from blue, and when in probe molecule solutions plus
When entering other metal ions, then without the generation of this phenomenon, this illustrates the absorption spectrum of the probe molecule to Zn2+There is uniqueness
Response.
As shown in Fig. 2, 10mL concentration be sequentially add 0.05 in 0.1mmol/L probe hhpa solution, 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、
1.2, 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 specrophotometer.As seen from Figure 2, with Zn2+Addition, solution
Absorbing wavelength is gradually blue shifted to 460nm by 580nm, works as Zn2+After additional amount reaches 1 times of mole of probe molecule, the suction of solution
It receives wavelength no longer to move, and the intensity of absorption peak is held essentially constant.This illustrates probe molecule hhpa and Zn2+It is that 1:1 is coordinated.
2, 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 have one compared with hypofluorescence emission peak at 665nm, excessive Zn is being added2+Afterwards, solution exists
At 665nm hypofluorescence emission peak disappear, and 585nm at appearance one very strong fluorescence emission peak, and be added 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,
0.8, 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 shown in the figure with Zn2+Concentration increase, 665nm place hypofluorescence emission peak gradually weakens finally disappear, and at 585nm appearance
One new fluorescence emission peak, and in Zn2+Additional amount reaches the 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
It Jia Ru not be dissolved with the metal ion (Ag of 10 times of moles+、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 that 10 times of moles are added2+, at excitation wavelength 460nm, launch wavelength 585nm, the fluorescence intensity of solution is measured, from figure
In 5 as can be seen that when largely there are other metal ions in solution, probe molecule hhpa is to Zn2+Selective recognition not
It is impacted.
As shown in fig. 6, adding in the mixed solution of the acetonitrile/water (v/v=1/2) of the probe molecule hhpa of 10 μm of ol/L
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 when minute.As shown in fig. 6, Zn is added 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 that 10mL concentration is 0.2-2 μm of ol/L (with 0.05 μm of ol/L increasing concen-trations)2+Acetonitrile/
The hhpa solution that 0.1mL concentration is 1mmol/L 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 within the scope of 0.2-1.1 μm of ol/L
Reveal good linear relationship (R2=0.9988), is limited to 1.26 × 10 using the resulting detection of 3 σ IUPAC criterion calculations-7mol/
L。
Claims (5)
1. a kind of preparation method of zinc ion probe, it is characterised in that:
Method includes the following steps:
Step 1: this method using chemical compounds I as raw material, is reacted with chloracetyl chloride under the action of alkalescent catalyst, is obtained
To compound ii;
Step 2: using potassium iodide as catalyst, under the conditions of existing for the acid binding agent, compound ii is reacted with salicylide hydrazone,
Obtain compound III;
First step reaction solvent used is methylene chloride, tetrahydrofuran, toluene.
First step reaction alkalescent catalyst used is any one in 4-dimethylaminopyridine, pyridine and triethylamine.
2. the preparation method of zinc ion probe according to claim 1, it is characterised in that: first step reaction temperature is -10
~0 DEG C.
3. the preparation method of zinc ion probe according to claim 1, it is characterised in that: second step reaction solvent used
For acetonitrile, ethyl alcohol, methylene chloride.
4. the preparation method of zinc ion probe according to claim 1, it is characterised in that: tie up acid used in second step reaction
Agent is at least one of potassium carbonate, sodium carbonate and triethylamine.
5. the preparation method of zinc ion probe according to claim 1, it is characterised in that: second step reaction temperature is heating
Reflux temperature.
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A near-infrared phenoxazinium-based fluorescent probe for zinc ions and its imaging in living cells;Qian-Qian Zhang et al.;《Sensors and Actuators B: Chemical》;20120616;第171-172卷;1001-1006 |
Phenoxazinone Synthase: Mechanism for the Formation of the Phenoxazinone Chromophore of Actinomycin;Clifton E. Barry, et al.;《Biochemistry》;19891231;第28卷;6323-6333 |
新型Cu2+离子荧光探针的合成及表征;陆春燕;《化学试剂》;20141231;第36卷(第12期);1117-1119 |
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