CN110229147A - A kind of cumarin-benzothiazolyl hydrazone compounds and its preparation method and application - Google Patents
A kind of cumarin-benzothiazolyl hydrazone compounds and its preparation method and application Download PDFInfo
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- CN110229147A CN110229147A CN201910540535.0A CN201910540535A CN110229147A CN 110229147 A CN110229147 A CN 110229147A CN 201910540535 A CN201910540535 A CN 201910540535A CN 110229147 A CN110229147 A CN 110229147A
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- benzothiazolyl
- cts
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 55
- 150000002500 ions Chemical class 0.000 claims abstract description 40
- 238000001514 detection method Methods 0.000 claims abstract description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 229910001868 water Inorganic materials 0.000 claims description 31
- 239000011259 mixed solution Substances 0.000 claims description 16
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims description 12
- -1 hydrazone compounds Chemical class 0.000 claims description 11
- PQMOXTJVIYEOQL-UHFFFAOYSA-N Cumarin Natural products CC(C)=CCC1=C(O)C(C(=O)C(C)CC)=C(O)C2=C1OC(=O)C=C2CCC PQMOXTJVIYEOQL-UHFFFAOYSA-N 0.000 claims description 10
- FSOGIJPGPZWNGO-UHFFFAOYSA-N Meomammein Natural products CCC(C)C(=O)C1=C(O)C(CC=C(C)C)=C(O)C2=C1OC(=O)C=C2CCC FSOGIJPGPZWNGO-UHFFFAOYSA-N 0.000 claims description 10
- 238000000862 absorption spectrum Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 5
- JOOMLFKONHCLCJ-UHFFFAOYSA-N N-(trimethylsilyl)diethylamine Chemical compound CCN(CC)[Si](C)(C)C JOOMLFKONHCLCJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- JYSUYJCLUODSLN-UHFFFAOYSA-N 1,3-benzothiazol-2-ylhydrazine Chemical compound C1=CC=C2SC(NN)=NC2=C1 JYSUYJCLUODSLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 229960004756 ethanol Drugs 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 238000007689 inspection Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 41
- 239000007850 fluorescent dye Substances 0.000 abstract description 23
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 238000004611 spectroscopical analysis Methods 0.000 abstract description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 abstract description 2
- 150000007857 hydrazones Chemical class 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 23
- 229910021645 metal ion Inorganic materials 0.000 description 21
- 239000010949 copper Substances 0.000 description 20
- 230000008859 change Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 229910001431 copper ion Inorganic materials 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 241000894007 species Species 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 206010034010 Parkinsonism Diseases 0.000 description 1
- 208000024777 Prion disease Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011981 development test Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000003068 molecular probe Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000007811 spectroscopic assay Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- 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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
-
- 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
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Abstract
The invention discloses a kind of cumarin-benzothiazolyl hydrazone compounds and its preparation method and application, wherein cumarin-benzothiazolyl hydrazone compounds structural formula are as follows:Hydrazone class fluorescent probe compounds of the present invention have multifunctionality, can be realized by UV-VIS spectrophotometry and fluorescent spectrometry to Cu2+The identification and quantitative detection of ion have good anti-interference, highly selective and sensitivity in the presence of other ions.
Description
Technical field
The present invention relates to a kind of cumarin-benzothiazolyl hydrazone compounds and its preparation method and application, belong to metal
Cu2+Ion detection and fluorescent molecular probe field.
Background technique
Metal ion is widely present in our living environment, is played in life system and its important function, with people
The health of class is closely bound up.Some metal ions can enter in life entity through various channels, and in life entity
Accumulation is got up, and the normal operation of life entity function is hindered, thus detect each metal ion species in the environment with the content in human body
It is most important.
Content of the copper ion in cell is only second to aluminium and iron, is essential minor metallic element, copper in life entity
With variable valence, a series of processes such as electron transmission, redox are participated in life entity；Excessive copper in the environment, meeting
Lead to serious environmental pollution, if there is excessive copper in human body, will lead to serious parkinson's syndrome and prion disease
Disease etc.；If there is too small amount of copper in human body, the physiological metabolism process that will lead to human normal hinders.Therefore, rationally
Detection copper ion content, it is necessary for establishing a kind of easy, sensitive method detection copper ion.
Currently, the method for detection copper ion has atomic absorption spectrum, inductively coupled plasma body-atomic emissions method, inductance
Coupled plasma-mass spectrography, electrochemical method etc..Although the detection sensitivity of these detection methods is very high, detected
Very accurate and expensive laboratory apparatus and cumbersome pretreatment etc. are needed in journey.
Fluorescent probe technique is because having the good, high sensitivity of selectivity, simple and quick and do not need by the excellent of expensive instrument
Put and be widely used in the detection of each metal ion species.It can be right using the relationship of ultraviolet/fluorescence property and ion concentration
Ion is quantitatively or qualitatively analyzed, convenient, fast, and selectivity with higher and sensitivity are very suitable for heavy metal
The real-time or in situ detection of ion.Based on the above reasons, various structure novels, highly selective copper ion fluorescence probe in recent years
It continues to bring out.
Summary of the invention
The present invention is intended to provide a kind of cumarin-benzothiazolyl hydrazone compounds and its preparation method and application.Due to
The factors such as the recognition performance of fluorescence probe and the space structure of probe molecule and recognition site are related, so the present invention is with cumarin
Group is fluorescent chromophore parent, has designed and synthesized the hydrazone compounds with-CH=N-NH- structure, while containing in molecule
There are O, S and N coordination atom, it can be with Ni metal2+Ion forms ligand molecule, generates specific ultraviolet and fluorescence phenomenon.
Cumarin of the present invention-benzothiazolyl hydrazone compounds, structural formula are as follows:
Cumarin of the present invention-benzothiazolyl hydrazone compounds preparation method, is by 2- hydrazinobenzothiazole and 3- aldehyde
Base -7-N, TMSDEA N diethylamine butylcoumariii are obtained by condensation reaction.Specifically comprise the following steps:
2.45g (10mmoL) 3- aldehyde radical -7-N, TMSDEA N diethylamine butylcoumariii and 1.65g (10mmoL) 2- diazanyl are weighed respectively
Benzothiazole is dissolved in 10mL dehydrated alcohol, and stirring dissolves it sufficiently；It is added in round-bottomed flask after acquired solution is mixed, and
0.5mL glacial acetic acid is added and makees catalyst, is warming up to 75 DEG C of back flow reaction 6h, is filtered after reaction solution is cooling, washing, drying, it is anhydrous
Ethyl alcohol recrystallization obtains yellow solid 2.50g, as target product, yield 70.4% after dry.
Synthetic route of the present invention is as follows:
Cumarin of the present invention-benzothiazolyl hydrazone compounds purposes is in qualitatively or quantitatively detection Cu2+Shi Zuowei inspection
Test agent application.
The application of cumarin of the present invention-benzothiazolyl hydrazone compounds is the progress ultraviolet-visible suction in water-bearing media
Spectroscopic assay is received, is realized by the variation of solution colour to Cu2+Qualitative or quantitative detection.
The water-bearing media is acetonitrile and the water mixed solution that 7:3 is constituted by volume.
The application of cumarin of the present invention-benzothiazolyl hydrazone compounds is the progress fluorescence spectrum survey in water-bearing media
It is fixed, it is realized by the variation of fluorescence intensity to Cu2+Qualitative or quantitative detection.
The water-bearing media is acetonitrile and the water mixed solution that 7:3 is constituted by volume.
There is-CH=N-NH- structure in target product of the present invention, containing substituted cumarin group and benzothiazole group,
Its molecular characterization is in the hydrazone compounds structure containing O, S and N coordination atom, can in water-bearing media with metal
Cu2+Ions binding forms ligand molecule, generates specific ultraviolet and fluorescence phenomenon.
Fluorescent probe compounds of the present invention can be used for Cu2+The identification and detection of ion have various metals ion stronger
Anti-interference ability, and fluorescent probe compounds of the present invention can be with Cu2+Ar ion mixing generates apparent color change phenomenon can be with
Realize naked eye identification and colorimetric analysis.
Test strips can be made to the Cu in water in the compounds of this invention CTS2+Ion carries out naked eye identification.The compounds of this invention
CTS can be also used for the Cu in biological cell2+Ion is detected.
Effect of the invention is embodied in:
Fluorescent probe compounds of the present invention have multifunctionality, can pass through UV-VIS spectrophotometry and fluorescence light
Spectrometry is realized respectively to Cu2+The identification of ion.Fluorescent probe compounds of the present invention can be used in aqueous medium to Cu2+From
The quick naked eye identification of son, quantitative detection, and to Cu2+Ion identification selectivity with higher and preferable anti-interference energy
Power, and naked eye identification and colorimetric analysis may be implemented in apparent color change phenomenon.Test strips experiment shows with the compound
The copper ion that the test strips of preparation can be used in qualitative detection water；The practicability of probe is probed into terms of biologic applications and is shown
The probe solution can detecting to the copper ion of cell exogenous.Above-mentioned experimental result illustrates our probe in environment
Have in monitoring and organism good using potential quality.
Detailed description of the invention
Fig. 1 is that the ultraviolet of different metal ions is added in compound CTS in the mixed solution that acetonitrile and water volume ratio are 7:3
Absorption spectrum.(illustration: the right side is CTS+Cu2+Color change, centre is that the color change of different metal ions is added in CTS,
A left side is the color of CTS solution).
Fig. 2 is that Cu is added2+The compound CTS of ion is inhaled in the mixed solution ultraviolet-visible that acetonitrile and water volume ratio are 7:3
Receive spectral derivative spectrogram.
Fig. 3 is metalloform-selective of the compound CTS in the mixed solution that acetonitrile and water volume ratio are 7:3 and resists dry
Disturb histogram；CTS is represented in acetonitrile and water volume ratio as the UV absorption intensity in the mixed solution of 7:3；Generation
The UV absorption intensity of different metal ions is added in table CTS in the mixed solution that acetonitrile and water volume ratio are 7:3；It represents
Different metal ions and Cu is added in the mixed solution that CTS acetonitrile and water volume ratio are 7:32+The UV absorption intensity of ion
(λmax=450nm).
Fig. 4 be fluorescent probe compounds CTS be added in the mixed solution that acetonitrile and water volume ratio are 7:3 different metal from
Fluorescence spectrum (the λ of sonex=459nm).(Cu attached drawing: is added2+(right side is for the color change image of CTS under ultraviolet light irradiation afterwards
CTS+Cu2+Color in the UV lamp, Zuo Wei CTS color in the UV lamp).
Fig. 5 is fluorescent probe compounds CTS Cu in the mixed solution that acetonitrile and water volume ratio are 7:32+Fluorescence titration
Spectrum (λex=459nm).
Fig. 6 is fluorescent probe compounds CTS metalloform-selective in the mixed solution that acetonitrile and water volume ratio are 7:3
With anti-interference histogram；CTS is represented in acetonitrile and water volume ratio as the fluorescence intensity in the mixed solution of 7:3；
Represent the fluorescence intensity that different metal ions are added in CTS solution；Represent the mixing as 7:3 in CTS acetonitrile and water volume ratio
It closes and different metal ions and Cu is added in solution2+Fluorescence intensity (the λ of ionem=532nm).
Fig. 7 is that fluorescence probe CTS detects Cu2+Practical application, under the conditions of naked eyes observation be added different metal ions it is molten
The filter paper color change of dipped probe solution after liquid, the right side are CTS+Cu2+Color change, centre be CTS in different gold is added
Belong to the color change of ion, the color of Zuo Wei CTS).
Fig. 8 is fluorescence probe CTS and Cu2+Job curve determination figure.
Fig. 9 is fluorescence probe CTS and Cu2+Complex compound mass spectrogram.
Figure 10 is the burnt development of figure Hela cell copolymerization: the first row is (1 μM) dyeing 30min of CTS；Second row is CTS+Cu2+
Dye 5min；It is successively from left to right: light field figure, dark field plot, stacking chart.
Specific embodiment
The present invention can be further illustrated by the following examples, but be not limited solely to embodiment.
Embodiment 1: the synthesis of compound CTS
2.45g (10mmoL) 3- aldehyde radical -7-N, TMSDEA N diethylamine butylcoumariii and 1.65g (10mmoL) 2- diazanyl are weighed respectively
Benzothiazole is dissolved in 10mL dehydrated alcohol, and stirring dissolves it sufficiently, and 0.5mL vinegar acid as catalyst is added, is warming up to 75 DEG C
Flow back 6h, filters after reaction solution is cooling, washing, drying, and dehydrated alcohol recrystallization obtains yellow solid 2.50g after dry, as
Target product, yield 70.4%.
FT-IR (KBr, cm-1): 3434.32 (- N-H), 2931,2872 (- CH3,-CH2), 1727 (- C=O), 1624 (- C
=N-), 1602 (- Ar), 1349 (- C-H), 1131 (- C-N), 638 (- N-H).
1H NMR(400MHz,DMSO-d6): δ (ppm) 8.24 (s, 1H), 8.14 (s, 1H), 7.78 (d, 1H, J=
8.0Hz), 7.64 (d, 1H, J=8.0Hz), 7.45 (d, 1H), 7.30 (t, 1H), 7.13 (t, 1H), 6.77 (d, 1H), 6.59
(s, 1H), 3.42 (m, 4H), 1.15 (t, 6H) .MS-ESI:m/z [M+H]+,393.26 for C21H20N4O2S.
Embodiment 2: the uv-visible absorption spectra measurement of compound CTS
Precise compound CTS 3.9mg, dissolving and being configured to concentration is 1.0 × 10-2The acetonitrile deposit of mol/L is molten
Liquid；It is 1.0 × 10 that stock solution is diluted to concentration by the mixed solution for being 7:3 with acetonitrile and water volume ratio-5Mol/L's is to be measured molten
Liquid.Taking 3mL concentration is 1.0 × 10-5The solution to be measured of mol/L (quartz colorimetric utensil with a thickness of 1cm) in quartz colorimetric utensil, so
After be separately added into 3 μ L concentration be 1.0 × 10-2Each metal ion species (Na of mol/L+, K+, Ag+, Ca2+, Mg2+, Pb2+, Li+, Al3 +, Zn2+, Cd2+, Cr3+, Cu2+, Ni2+, Co2+, Fe3+, Hg2+) aqueous solution, shake up, after 1 minute measure solution ultraviolet-visible
Absorption spectrum (see attached drawing Fig. 1).Before metal ion is added, the uv-visible absorption spectra of compound CTS, which is shown in 459nm, to be had
One apparent absorption peak, as addition Cu2+After ion, absorption peak of the CTS at 459nm weakens, and occurs one at 450nm
New absorption peak, solution colour also become greenish orange red (as shown in attached drawing illustration) from yellow green, can visually observe, have
There is " naked eye identification " function, compound CTS can be used as ultraviolet identification and naked eye identifies Cu2+The colorimetric probe of ion；And in phase
With under the conditions of, other metal ions such as: Na+, K+, Ag+, Ca2+, Mg2+, Pb2+, Li+, Al3+, Zn2+, Cd2+, Cr3+, Ni2+, Co2+,
Fe3+, Hg2+The addition uv-visible absorption spectra big to CTS all have no significant effect, there is no becoming substantially for solution colour
Change.
Embodiment 3: the measurement of the uv-visible absorption spectra titration experiments and detection limit of compound CTS
Taking 3mL concentration is 1.0 × 10-5The solution to be measured of mol/L in quartz colorimetric utensil, be separately added into 3,6,9,12,15,
18,21,24,27,30 μ L isoconcentrations are 1.0 × 10-3The Cu of mol/L2+Deionized water solution, after shaking up measure solution it is ultraviolet-can
Such as absorption spectrum (such as shown in attached drawing Fig. 2).With Cu2+The addition of ion, absorbance of the compound CTS at 459nm gradually subtract
It is weak and be blue shifted at 450nm, and occur an apparent isocenter at 450nm, illustrate in acetonitrile and water volume ratio for 7:3's
Compound CTS energy and Cu in mixed solution2+Ion forms stable complex, Cu2+Ion is 1.0 × 10-6~1.6 × 10- 5Within the scope of mol/L, Cu2+Ion concentration is in preferable linear relationship (R with absorbance change amount at 450nm2=0.98), pass through
Compound CTS is calculated to Cu2+The detection of ion is limited to 2.40 × 10-6mol/L。
Embodiment 4: fluorescent probe compounds CTS is to Cu2+The selectivity and anti-interference of ion identification
Taking 3mL concentration is 1.0 × 10-6The solution to be measured of mol/L in quartz colorimetric utensil, be added 3 μ L concentration be 1.0 ×
10-2The Cu of mol/L2+After ion, then being separately added into 3 μ L concentration is 1.0 × 10-2Each metal ion species (Na of mol/L+, K+, Ag+, Ca2+, Mg2+, Pb2+, Li+, Al3+, Zn2+, Cd2+, Cr3+, Ni2+, Co2+, Fe3+, Hg2+) solution, it shakes up, measures it after twenty minutes
Ultra-violet absorption spectrum (as shown in attached drawing Fig. 3), is added other metal ions such as: Na as the result is shown+, K+, Ag+, Ca2+, Mg2+, Pb2 +, Li+, Al3+, Zn2+, Cd2+, Cr3+, Ni2+, Co2+, Fe3+, Hg2+Deng the uv absorption property to fluorescent probe compounds CTS
It has little effect, this has indicated that fluorescent probe compounds CTS to Cu2+Ion identification selectivity with higher and preferable
Anti-interference ability.
Embodiment 5: the fluorescence spectrometry of fluorescent probe compounds CTS
Taking 3mL concentration is 1.0 × 10-6The solution to be measured of mol/L is then respectively adding 3 μ L concentration in quartz colorimetric utensil
It is 1.0 × 10-2Each metal ion species (Na of mol/L+, K+, Ag+, Ca2+, Mg2+, Pb2+, Li+, Al3+, Zn2+, Cd2+, Cr3+, Ni2 +, Co2+, Fe3+, Hg2+) solution, it shakes up, it is (such as attached to measure its fluorescence emission spectrum after 1 minute under the excitation wavelength of λ=459nm
Shown in figure Fig. 4), as the result is shown when no addition metal ion, fluorescent probe compounds CTS has a stronger at λ=532nm
Fluorescence peak, Cu2+Compound CTS forms a new fluorescence peak, K at 513nm after ion is added+, Ag+, Ca2+, Mg2+, Pb2+,
Li+, Al3+, Zn2+, Cd2+, Cr3+, Ni2+, Fe3+It is had little effect Deng the fluorescence property to fluorescent probe compounds CTS；Co2 +, Hg2+Make the fluorescent weakening half or so of fluorescence probe CTS, while can see solution under the irradiation of 365nm fluorescent lamp
Significant change occurs for color, becomes colourless (as shown in 4 illustration of attached drawing) as yellow green.
Embodiment 6: the fluorescence spectroscopic titration experiment of fluorescent probe compounds CTS
Taking 3mL concentration is 1.0 × 10-6The solution to be measured of mol/L in quartz colorimetric utensil, be separately added into 3,6,9,12,15,
18,21,24,27,30 μ L isoconcentrations are 1.0 × 10-3The Cu of mol/L2+Deionized water solution shakes up, and the glimmering of solution is measured after balance
Light spectrum (as shown in figure 5 of the drawings), with Cu2+The addition of ion, compound CTS is in λemFluorescence intensity at=532nm is gradually
Weaken, final Cu2+Addition, quench the fluorescence of fluorescence probe CTS almost.
Embodiment 7: fluorescent probe compounds CTS is to Cu2+The selectivity and anti-interference of ion identification
Taking 3mL concentration is 1.0 × 10-6The solution to be measured of mol/L in quartz colorimetric utensil, be added 3 μ L concentration be 1.0 ×
10-2The Cu of mol/L2+After ion, then being separately added into 3 μ L concentration is 1.0 × 10-2Each metal ion species (Na of mol/L+, K+, Ag+, Ca2+, Mg2+, Pb2+, Li+, Al3+, Zn2+, Cd2+, Cr3+, Ni2+, Co2+, Fe3+, Hg2+) solution, shake up, after twenty minutes λ=
Its fluorescence emission spectrum (as shown in attached drawing Fig. 6) is measured under the excitation wavelength of 459nm, and other metal ions are added as the result is shown
Such as: Na+, K+, Ag+, Ca2+, Mg2+, Pb2+, Li+, Al3+, Zn2+, Cd2+, Cr3+, Ni2+, Co2+, Fe3+, Hg2+Deng to fluorescence probe
The fluorescence intensity of compound CTS has little effect, this has indicated that fluorescent probe compounds CTS to Cu2+Ion identification has
Higher selectivity and preferable anti-interference ability.
Embodiment 8: fluorescent probe compounds CTS is to Cu2+The practical application of ion identification
Precise fluorescent probe compounds CTS 0.393g, dissolving and being configured to concentration is 1.0 × 10-1The two of mol/L
Chloromethanes stock solution；Clean filter paper is made to the sequin of appropriate size of punch, then sequin is immersed and is prepared
In good stock solution, impregnate sequin sufficiently, white filter paper leaching is yellow, takes out after five minutes and is put into baking oven drying
Spare, then 3 μ L concentration are 1.0 × 10 on sequin respectively-2Each metal ion species (Na of mol/L+, K+, Ag+, Ca2+, Mg2 +, Pb2+, Li+, Al3+, Zn2+, Cd2+, Cr3+, Cu2+, Ni2+, Co2+, Fe3+, Hg2+) aqueous solution, observe sequin color become
Change.As a result as shown in fig. 7, Na is added+, K+, Ag+, Ca2+, Mg2+, Pb2+, Li+, Al3+, Zn2+, Cd2+, Cr3+, Ni2+, Co2+, Fe3 +, Hg2+After solion, the color of sequin hardly happens variation, as addition Cu2+After ion, the color of sequin is by yellow
Become orange.
Embodiment 9: fluorescent probe compounds CTS is to Cu in cell2+Ion fluorescence development test
The practicability for exploring the bio-imaging of probe CTS, can promote the detection in biology.Well-grown Hela is thin
Born of the same parents carry out cell imaging test after (1 μM) processing cell 30min of fluorescence probe CTS, and Cu is added in subsequent culture dish2+(10μM)
After cultivating 5min, cell imaging test is carried out.By attached drawing 8 it is found that cell does not issue fluorescence before probe CTS solution is not added；Add
After entering probe CTS culture, probe CTS has good permeability, it can be observed that cell has stronger green fluorescence；It is cultivating again
Cu is added in ware2+After (10 μM), observe that the stronger green fluorescence of cell weakens, until all disappearing.These phenomenons and spectrum
Data is consistent.Apparent change in fluorescence shows that probe CTS can monitor Cu2+Presence in biosystem.
Embodiment 10: fluorescent probe compounds CTS is to Cu2+The Mechanism Study of ion identification
Precise fluorescent probe compounds CTS 0.39mg, dissolving and being configured to concentration is 1.0 × 10-3The second of mol/L
The stock solution that nitrile and water volume ratio are 7:3；Keep Cu2+It is constant with the amount of the total material of CTS solution, change Cu2+Concentration,
So that the concentration and Cu of CTS solution to be tested2+The mass ratio of the material of concentration is respectively 10:0,9:1,8:2,7:3,6:4,5:5,4:
6,3:7,2:8,1:9,0:10 measure 30 μ L, 27 μ L, 24 μ L, 21 μ L, 18 μ L, 15 μ L, 12 μ L, 9 μ L, 6 μ L, 3 μ L, 0 μ L
CTS testing sample solution, thereto it is corresponding be added dropwise 0 μ L, 3 μ L, 6 μ L, 9 μ L, 12 μ L, 15 μ L, 18 μ L, 21 μ L, 24 μ L, 27 μ L,
30μL 1.0×10-3Mol/L Ni metal2+Solution is then that 7:3 mends above-mentioned solution with acetonitrile and water volume ratio in PE pipe
It is added to 3mL.With the variation of fluorescence spectrum to Cu2+It carries out concentration titrations and tests its determining Job curve.With probe or detection ion
Molar ratio be horizontal coordinate, be that vertical coordinate is mapped with the intensity of variation, level corresponding to the maximum point of spectrum change
Coordinate is exactly the coordination ratio of CTS probe molecule and detection ion.[Cu is found as shown in Figure 92+]/[CTS]+[Cu2+When]=0.5,
There is inflection point, shows CTS and Cu2+Ion is complexed with 1:1, i.e. CTS and Cu2+Between the stoichiometric ratio that is complexed be
1:1.The mass spectroscopy result m/z of Figure 10 is 455.335, in conjunction with Job curve it is found that fluorescence probe CTS and Cu2+It is with 1:1
Combination forms complex compound.
Claims (9)
1. a kind of cumarin-benzothiazolyl hydrazone compounds, it is characterised in that: the cumarin-benzothiazolyl hydrazone class
Closing object is the hydrazone compounds with-C=N-NH- structure, while containing coordination atoms such as O, S and N in molecule, can be with metal
Cu2+Ion coordination forms complex, generates specific ultraviolet and fluorescence phenomenon.
2. cumarin according to claim 1-benzothiazolyl hydrazone compounds, it is characterised in that its structural formula is as follows:
3. a kind of preparation method of cumarin as claimed in claim 2-benzothiazolyl hydrazone compounds, it is characterised in that: be
By 2- hydrazinobenzothiazole and 3- aldehyde radical -7-N, TMSDEA N diethylamine butylcoumariii condensation reaction obtains target product.
4. preparation method according to claim 3, it is characterised in that include the following steps:
Weigh 2.45g3- aldehyde radical -7-N respectively, it is anhydrous that TMSDEA N diethylamine butylcoumariii with 1.65g2- hydrazinobenzothiazole is dissolved in 10mL
In ethyl alcohol, stirring dissolves it sufficiently；It is added in round-bottomed flask after acquired solution is mixed, and 0.5mL glacial acetic acid is added and urges
Agent is warming up to 75 DEG C of back flow reaction 6h, and suction filtration, washing, drying after reaction solution is cooling, dehydrated alcohol recrystallization obtain after dry
To yellow solid, as target product.
5. a kind of purposes of cumarin of any of claims 1 or 2-benzothiazolyl hydrazone compounds, it is characterised in that: be
Qualitative or quantitative detection Cu2+Shi Zuowei detection reagent application.
6. a kind of application of cumarin of any of claims 1 or 2-benzothiazolyl hydrazone compounds, it is characterised in that: be
Uv-visible absorption spectra measurement is carried out in water-bearing media, is realized by the variation of solution colour to Cu2+Qualitative or quantitative inspection
It surveys.
7. application according to claim 6, it is characterised in that:
The water-bearing media is acetonitrile and the water mixed solution that 7:3 is constituted by volume.
8. a kind of application of cumarin of any of claims 1 or 2-benzothiazolyl hydrazone compounds, it is characterised in that: be
Fluorescence spectrometry is carried out in water-bearing media, is realized by the variation of fluorescence intensity to Cu2+Qualitative or quantitative detection.
9. application according to claim 8, it is characterised in that:
The water-bearing media is acetonitrile and the water mixed solution that 7:3 is constituted by volume.
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| CN111662279A (en) * | 2020-07-20 | 2020-09-15 | 安徽大学 | Naphthalene-substituted carbazole-benzothiazolyl hydrazone compound and preparation method and application thereof |
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| CN113121513A (en) * | 2021-04-26 | 2021-07-16 | 安徽大学 | Carbazole-coumarin hydrazone compound and preparation method and application thereof |
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