CN107698627B - A kind of preparation method of multi signal probe - Google Patents
A kind of preparation method of multi signal probe Download PDFInfo
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- CN107698627B CN107698627B CN201710943821.2A CN201710943821A CN107698627B CN 107698627 B CN107698627 B CN 107698627B CN 201710943821 A CN201710943821 A CN 201710943821A CN 107698627 B CN107698627 B CN 107698627B
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- signal probe
- multi signal
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- deicer
- acid
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- 239000000523 sample Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000012445 acidic reagent Substances 0.000 claims abstract description 11
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 8
- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical compound N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 claims abstract description 6
- MBVFRSJFKMJRHA-UHFFFAOYSA-N 4-fluoro-1-benzofuran-7-carbaldehyde Chemical compound FC1=CC=C(C=O)C2=C1C=CO2 MBVFRSJFKMJRHA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 10
- 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 description 10
- 239000002808 molecular sieve Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 238000013459 approach Methods 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 28
- 238000001514 detection method Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 abstract description 2
- PMWXGSWIOOVHEQ-UHFFFAOYSA-N pyridine-2,6-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=N1 PMWXGSWIOOVHEQ-UHFFFAOYSA-N 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 41
- 239000000243 solution Substances 0.000 description 33
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000011701 zinc Substances 0.000 description 11
- 239000012043 crude product Substances 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000083 pulse voltammetry Methods 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000003115 supporting electrolyte Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 206010060862 Prostate cancer Diseases 0.000 description 1
- 208000000236 Prostatic Neoplasms Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000036528 appetite Effects 0.000 description 1
- 235000019789 appetite Nutrition 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
- 238000011161 development Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 208000033065 inborn errors of immunity Diseases 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus 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
- 230000022983 regulation of cell cycle Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
-
- 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
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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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- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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Abstract
The invention discloses a kind of preparation methods of zinc ion multi signal probe, belong to environmental testing.The preparation method is that under the conditions of existing for acid reagent and deicer, 2,6 pyridine dialdehyde are reacted with diaminomaleonitrile, and product is prepared and is reacted again with ferrocene carboxaldehyde, and zinc ion multi signal probe of the present invention is prepared.Multi signal probe molecule preparation method provided by the present invention is simple, is easy to industrialized production.And the multi signal probe that is prepared is low to the detection limit of zinc ion and high selectivity.
Description
The application is：On April 19th, 2017, application No. is：201710256229.5, it is entitled：It is a kind of more
The divisional application of the patent of invention of signal probe and its preparation method and application.
Technical field
The invention belongs to environmental testings, and in particular to a kind of multi signal probe and its preparation method and application can be used
The measurement of zinc ion in environment.
Background technology
Zn2+It is a kind of indispensable trace element in organism, widely exists in cell and body fluid, is sent out in growth
Educate, reproduction, nerve signal transmission, gene typing, nucleic acid recognizing, cell cycle regulation, Zn in the physiology courses such as apoptosis2+With weight
It acts on.Zn2+Intake it is excessive or the insufficient growth and development that can all make organism is disorderly, cause a variety of diseases, under appetite
The diseases such as drop, hypoimmunity, diabetes, prostate cancer are all unbalance related with zinc ion.Therefore how Zn is effectively detected2+It is right
All have great importance in bioscience and environmental science etc..
Invention content
The present invention be directed to above-mentioned problems to provide a kind of multi signal probe and its preparation for detecting zinc ion
Method and purposes.
The purpose of the present invention can be achieved through the following technical solutions：、
A kind of multi signal probe, the structural formula of the probe are as follows：
A kind of preparation method of multi signal probe described above, the reaction route of this method are as follows：
In some specific technical solutions：This approach includes the following steps：
The first step：Under the conditions of existing for acid reagent and deicer, chemical compounds I is reacted with diaminomaleonitrile,
Compound III is prepared；
Second step：Under the conditions of existing for acid reagent and deicer, compound III is reacted with ferrocene carboxaldehyde, system
It is standby to obtain compounds Ⅳ.
In some preferred technical solutions：Acid reagent described in the first step and second is glacial acetic acid, hydrochloric acid, sulfuric acid
Or phosphoric acid.
In some preferred technical solutions：Deicer described in the first step and second step is molecular sieve or anhydrous sulphur
Sour sodium.
In some preferred technical solutions：In the first step：In the first step：The Molar of acid reagent and chemical compounds I
It is 40~100L/mol than ratio, the molal ratio of deicer and chemical compounds I is 1000~4000g/mol.
In some preferred technical solutions：In second step：Acid reagent and the Molar of compound III ratio be 70~
The molal ratio of 160L/mol, deicer and chemical compounds I is 1200~6000g/mol.
In technical solution of the present invention：The molar ratio of chemical compounds I and diaminomaleonitrile is 1：2~6.
In technical solution of the present invention：Compound III and the molar ratio of ferrocene carboxaldehyde are 1：2~6.
In some preferred technical solutions：The first step and the reaction temperature of second step are to be heated to reflux temperature.
In technical solution of the present invention：Application of the multi signal probe as detection zinc ion；It is preferred that more letters
The application as detection zinc ion in the environment of number probe.
Beneficial effects of the present invention：
Multi signal probe molecule preparation method provided by the present invention is simple, is easy to industrialized production.And be prepared
Multi signal probe is low to the detection limit of zinc ion and high selectivity.
Description of the drawings
Fig. 1 is multi signal probe to Zn2+Selective recognition abosrption spectrogram.
Fig. 2 is Zn2+Figure is titrated to the absorption spectrum of multi signal probe.
Fig. 3 is multi signal probe to Zn2+Selective recognition DPV figure.
Fig. 4 is Zn2+Figure is titrated to the DPV of multi signal probe.
Fig. 5 is Zn2+Figure is titrated to the CV of multi signal probe.
Specific implementation mode
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
Sequentially added in the three-neck flask of 250mL absolute ethyl alcohol (50mL), 2,6- pyridines dialdehyde (0.135g, 1mmol),
Glacial acetic acid (0.1mL) and anhydrous sodium sulfate (1g), are heated to reflux.It is being passed through N2Under conditions of, it is slowly added dropwise with constant pressure funnel molten
The 50mL ethanol solutions for having diaminomaleonitrile (0.216g, 2mmol), the reaction was continued after being added dropwise, TLC monitoring reactions
Process waits for being filtered to remove sodium sulphate while hot after reaction, filtrate is rotated and is evaporated to obtain white solid, by the anhydrous second of crude product
Alcohol recrystallizes, and obtains White crystalline product 0.29g, yield 94.2%, purity 99.46%.
Elemental analysis：(%) for C15H9N9:Calculated value：C 57.14；H 2.88；N 39.98, measured value：C
54.37；H 2.78；N 38.71.
IR(KBr),ν,cm-1:3327,3210,2234,1578,1460,1285,1147,981,741。
1H NMR(500MHz,CDCl3,TMS):δ=5.17 (s, 4H, NH2), 8.04 (d, J=8.0,2H, Py-H),
8.19 (t, J=7.4,1H, Py-H), 8.37 (s, 2H, N=CH) ppm.
Absolute ethyl alcohol (30mL), compound III (0.157g, 0.5mmol), ice are sequentially added in the three-neck flask of 100mL
Acetic acid (0.08mL) and anhydrous sodium sulfate (0.6g), are heated to reflux.It is being passed through N2Under conditions of, it is slowly added dropwise with constant pressure funnel molten
The 50mL ethanol solutions for having ferrocene carboxaldehyde (0.214g, 1mmol), be added dropwise after the reaction was continued, TLC monitoring react into
Journey waits for being filtered to remove sodium sulphate while hot after reaction, filtrate is rotated and is evaporated to obtain dark red solid, by the anhydrous second of crude product
Alcohol recrystallizes, and obtains red crystals product 0.34g, yield 92.6%, purity 99.38%.
Elemental analysis：(%) for C37H25N9Fe2:Calculated value：C 62.83；H 3.56；N 17.82, measured value：C
62.67；H3.69；N 17.94.
IR (KBr), ν, cm-1：3334,3228,2239,1561,1517,1361,1307,997,791,732.
1H NMR(500MHz,CDCl3,TMS)：δ=4.32 (s, 10H, Cp-H), 4.57 (t, J=7.6,4H, Cp-H),
4.69 (t, J=7.6,4H, Cp-H), 8.05 (d, J=8.0,2H, Py-H), 8.21 (t, J=7.4,1H, Py-H), 8.39 (s,
2H, N=CH), 8.44 (s, 2H, N=CH) ppm.
Embodiment 2
Sequentially added in the three-neck flask of 250mL absolute ethyl alcohol (50mL), 2,6- pyridines dialdehyde (0.135g, 1mmol),
Concentrated hydrochloric acid (0.08mL) and anhydrous sodium sulfate (1.5g), are heated to reflux.It is being passed through N2Under conditions of, it is slowly added dropwise with constant pressure funnel
Dissolved with the 50mL ethanol solutions of diaminomaleonitrile (0.324g, 3mmol), the reaction was continued after being added dropwise, and TLC monitorings are anti-
Process is answered, waits for being filtered to remove sodium sulphate while hot after reaction, filtrate rotation is evaporated to obtain white solid, by crude product with anhydrous
Ethyl alcohol recrystallization obtains White crystalline product 0.30g, yield 93.7%, purity 99.93%.
Absolute ethyl alcohol (30mL), compound III (0.157g, 0.5mmol), dense is sequentially added in the three-neck flask of 100mL
Hydrochloric acid (0.08mL) and anhydrous sodium sulfate (1g), are heated to reflux.It is being passed through N2Under conditions of, with constant pressure funnel be slowly added dropwise dissolved with
The 50mL ethanol solutions of ferrocene carboxaldehyde (0.321g, 1.5mmol), be added dropwise after the reaction was continued, TLC monitoring react into
Journey waits for being filtered to remove sodium sulphate while hot after reaction, filtrate is rotated and is evaporated to obtain dark red solid, by the anhydrous second of crude product
Alcohol recrystallizes, and obtains red crystals product 0.33g, yield 91.5%, purity 99.88%.
Embodiment 3
Sequentially added in the three-neck flask of 250mL absolute ethyl alcohol (50mL), 2,6- pyridines dialdehyde (0.135g, 1mmol),
The concentrated sulfuric acid (0.05mL) and molecular sieve (2g), are heated to reflux.It is being passed through N2Under conditions of, it is slowly added dropwise dissolved with two with constant pressure funnel
The 50mL ethanol solutions of amino Maleic nitrile (0.432g, 4mmol), be added dropwise after the reaction was continued, TLC monitoring react into
Journey waits for being filtered to remove molecular sieve while hot after reaction, filtrate is rotated and is evaporated to obtain white solid, by crude product absolute ethyl alcohol
Recrystallization, obtains White crystalline product 0.29g, yield 90.1%, purity 99.91%.
Absolute ethyl alcohol (30mL), compound III (0.157g, 0.5mmol), dense is sequentially added in the three-neck flask of 100mL
Sulfuric acid (0.04mL) and molecular sieve (1.5g), are heated to reflux.It is being passed through N2Under conditions of, it is slowly added dropwise dissolved with two with constant pressure funnel
The 50mL ethanol solutions of luxuriant armor aldehyde (0.428g, 2mmol), the reaction was continued after being added dropwise, and TLC monitors reaction process,
It waits for being filtered to remove molecular sieve while hot after reaction, filtrate rotation is evaporated to obtain dark red solid, by crude product absolute ethyl alcohol
Recrystallization, obtains red crystals product 0.31g, yield 91.4%, purity 99.42%.
Embodiment 4
Sequentially added in the three-neck flask of 250mL absolute ethyl alcohol (50mL), 2,6- pyridines dialdehyde (0.135g, 1mmol),
Phosphoric acid (0.04mL) and molecular sieve (4.0g), are heated to reflux.It is being passed through N2Under conditions of, it is slowly added dropwise dissolved with two with constant pressure funnel
The 50mL ethanol solutions of amino Maleic nitrile (0.648g, 6mmol), be added dropwise after the reaction was continued, TLC monitoring react into
Journey waits for being filtered to remove molecular sieve while hot after reaction, filtrate is rotated and is evaporated to obtain white solid, by crude product absolute ethyl alcohol
Recrystallization, obtains White crystalline product 0.29g, yield 90.8%, purity 99.87%.
Absolute ethyl alcohol (30mL), compound III (0.157g, 0.5mmol), phosphorus are sequentially added in the three-neck flask of 100mL
Sour (0.035mL) and molecular sieve (3.0g), are heated to reflux.It is being passed through N2Under conditions of, it is slowly added dropwise dissolved with two with constant pressure funnel
The 50mL ethanol solutions of luxuriant armor aldehyde (0.642g, 3mmol), the reaction was continued after being added dropwise, and TLC monitors reaction process,
It waits for being filtered to remove molecular sieve while hot after reaction, filtrate rotation is evaporated to obtain dark red solid, by crude product absolute ethyl alcohol
Recrystallization, obtains red crystals product 0.33g, yield 92.8%, purity 99.46%.
Property experiment
Multi signal probe is all made of what embodiment 1 was prepared used in absorption spectrum experiment below and electrochemistry use
Multi signal probe.
1, absorption spectrum is tested
Fig. 1 is multi signal probe to Zn2+Selective recognition abosrption spectrogram.In the multi signal probe of 10 μm of ol/L
Acetonitrile/water (4:1, v:V) metal ion (Zn of 2 times of amounts is separately added into mixed solution2+、Na+、Ag+、Mg2+、Ca2+、Pb2+、
Co2+、Cd2+、Cu2+、Ni2+、Fe2+、Al3+).Absorption spectrum is surveyed on Shimadzu UV2450 type ultraviolet-uisible spectrophotometers
.
As can be seen from Figure 1 Zn is added in solution system2+Afterwards, significant change occurs for the absorption curve of solution, originally
Absorption peak strength reduces at 265nm, at the absorption peak strength enhancing and red shift (24nm) to 326nm at 302nm, at 460nm
Absorption peak strength reduces.And after other metal ions are added, the absorption curve of solution does not change significantly.This illustrates this
Multi signal probe in the solution can Selective recognition Zn2+。
Fig. 2 is Zn2+Figure is titrated to the absorption spectrum of multi signal probe.In the acetonitrile/water of the multi signal probe of 10 μm of ol/L
(4:1, v:V) in mixed solution, 0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.5 and are separately added into
The Zn of 2.0 times of amounts2+.Absorption spectrum measures on Shimadzu UV2450 type ultraviolet-uisible spectrophotometers.
From figure 2 it can be seen that during titration, absorption peak strength continuously decreases at 265nm, the suction at 302nm
It receives peak intensity to gradually increase at simultaneously red shift (24nm) to 326nm, absorption peak strength continuously decreases at 460nm.The face of solution simultaneously
Color gradually becomes purple by yellow, illustrates that the multi signal probe can be used for realizing open hole detection Zn2+。
2, electrochemistry experiment
Fig. 3 is multi signal probe to Zn2+Selective recognition DPV figure.In a concentration of 0.1mmol/L multi signals probes of 10mL
Metal ion solution (the Zn of 10 a concentration of 0.1mol/L of μ L (1 times of mole) is separately added into solution2+、Na+、Ag+、Mg2+、
Ca2+、Pb2+、Co2+、Cd2+、Cu2+、Ni2+、Fe2+、Al3+).Solution system used in experiment is acetonitrile/water (4:1, v:
V) mixed solution, n-Bu4NPF6It is work using platinum disk electrode that (0.1mol/L), which is used as supporting electrolyte, three-electrode system,
Electrode, platinum electrode are auxiliary electrode, and Ag/AgCl electrodes are reference electrode, and measuring temperature is 25 DEG C, and solution divides in logical nitrogen 30
It is measured after clock.Conventional difference pulse voltammetry (DPV) measures on CHI660C type electrochemical workstations.
Conventional difference pulse voltammetry (DPV) response shows a reversible one-electron oxidation process, half wave potential
(E1/2) it is 0.38V, belong to Fc+The redox peaks of/Fc.After the metal ion of one times of amount is added under these experimental conditions,
It was found that Zn only is being added2+Afterwards, the peak at 0.38V disappears, and occurs a new peak at 0.42V.And be added other metals from
Then without this phenomenon after son, this illustrates multi signal probe to Zn2+There is unique electrochemical response.
Fig. 4 is Zn2+Figure is titrated to the DPV of multi signal probe.In a concentration of 0.1mmol/L multi signals probe solutions of 10mL
Sequentially add the Zn of 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.5,2.0 times of amount2+.Used in experiment
Solution system be acetonitrile/water (4:1, v:V) mixed solution, n-Bu4NPF6(0.1mol/L) be used as supporting electrolyte, three
Electrode system is working electrode using platinum disk electrode, and platinum electrode is auxiliary electrode, and Ag/AgCl electrodes are reference electrode, are surveyed
Constant temperature degree is 25 DEG C, and solution is measured in logical nitrogen after 30 minutes.Conventional difference pulse voltammetry (DPV) is in CHI660C types
It is measured on electrochemical workstation.
With Zn it can be seen from Fig. 42+Addition, Fc+The redox peaks of/Fc are gradually moved to from 0.38V
At 0.42V, and continuously decrease.Work as Zn2+After addition reaches one times of amount of probe molecule, Fc+The redox peaks of/Fc no longer occur
Displacement, and the intensity at peak is basically unchanged.This illustrates multi signal probe and Zn2+It is 1:1 coordination.
Fig. 5 is Zn2+Figure is titrated to the CV of multi signal probe.In a concentration of 0.1mmol/L multi signals probe solutions of 10mL
Sequentially add the Zn of 0,0.2,0.4,0.6,0.8,1.0,1.5,2.0 times of amount2+.Solution system used in experiment is second
Nitrile/water (4:1, v:V) mixed solution, n-Bu4NPF6(0.1mol/L) is used as supporting electrolyte, three-electrode system to justify using platinum
Disc electrode is working electrode, and platinum electrode is auxiliary electrode, and Ag/AgCl electrodes are reference electrode, sweep speed 100mV/s,
Measuring temperature is 25 DEG C, and solution is measured in logical nitrogen after 30 minutes.Cyclic voltammetry (CV) is in CHI660C type electrochemistry works
It stands upper measurement.
From fig. 5, it can be seen that with Zn2+Addition, half wave potential E in cyclic voltammogram1/2Shuffle 55mV, and
The Zn of one times of amount is added2+Half wave potential E afterwards1/2Substantially it no longer moves.This is because Zn2+1 is formd with multi signal probe:1
Complex increases the drawing electronic capability of ferrocene so that ferrocene is more difficult to be aoxidized.
Claims (6)
1. the preparation method of multi signal probe shown in a kind of formula IV, it is characterised in that：
This approach includes the following steps：
The first step：Under the conditions of existing for acid reagent and deicer, chemical compounds I is reacted with diaminomaleonitrile, is prepared
Obtain compound III；
Second step：Under the conditions of existing for acid reagent and deicer, compound III is reacted with ferrocene carboxaldehyde, is prepared into
To compounds Ⅳ；
Wherein, the acid reagent is that either the phosphoric acid deicer is molecular sieve or nothing for glacial acetic acid, hydrochloric acid, sulfuric acid
Aqueous sodium persulfate.
2. the preparation method of multi signal probe according to claim 1, it is characterised in that：In the first step：Acid reagent with
The Molar ratio of chemical compounds I is 40~100L/mol.
3. the preparation method of multi signal probe according to claim 1, it is characterised in that：In the first step：Deicer and change
The molal ratio for closing object I is 1000~4000g/mol.
4. the preparation method of multi signal probe according to claim 1, it is characterised in that：In second step：Acid reagent with
The Molar ratio of chemical compounds I is 70~160L/mol.
5. the preparation method of multi signal probe according to claim 1, it is characterised in that：In second step：Deicer and change
Conjunction III molal ratio of object is 1200~6000g/mol.
6. the preparation method of multi signal probe according to claim 1, it is characterised in that：The reaction of the first step and second step
Temperature is to be heated to reflux temperature.
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| CN104004028A (en) * | 2014-06-06 | 2014-08-27 | 南京工业大学 | Multichannel molecular probe for detecting Hg<2+> and preparation method thereof |
| CN105820811A (en) * | 2016-04-28 | 2016-08-03 | 南京晓庄学院 | Fluorescent probe, and synthesis method and application thereof |
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| CN101613344B (en) * | 2008-06-25 | 2012-09-12 | 中国科学院理化技术研究所 | Fluorescent probe for selectively detecting zinc ions in cells, synthesizing method thereof and application thereof |
| JP5636644B2 (en) * | 2009-07-02 | 2014-12-10 | 国立大学法人 奈良先端科学技術大学院大学 | Zinc luminescent probe and illuminant |
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| KR101742782B1 (en) * | 2015-07-02 | 2017-06-01 | 공주대학교 산학협력단 | New triazolothiadiazole compound, uses thereof, and organic electroluminescent devices having the same |
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| CN105820811A (en) * | 2016-04-28 | 2016-08-03 | 南京晓庄学院 | Fluorescent probe, and synthesis method and application thereof |
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