CN109665975A - The preparation method of Salen ligand with cis-trans isomerism and its in Cu2Application in+probe and pH probe - Google Patents
The preparation method of Salen ligand with cis-trans isomerism and its in Cu2Application in+probe and pH probe Download PDFInfo
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- 239000003446 ligand Substances 0.000 title claims abstract description 39
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000000523 sample Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000001514 detection method Methods 0.000 claims abstract description 18
- 238000004847 absorption spectroscopy Methods 0.000 claims abstract description 13
- 238000010791 quenching Methods 0.000 claims abstract description 10
- 230000000171 quenching effect Effects 0.000 claims abstract description 10
- 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 7
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000004440 column chromatography Methods 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 229960004756 ethanol Drugs 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000001917 fluorescence detection Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000000862 absorption spectrum Methods 0.000 claims description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000004699 copper complex Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 238000002189 fluorescence spectrum Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 241000219000 Populus Species 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 210000000805 cytoplasm Anatomy 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- -1 metals ion Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000000954 titration curve Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/30—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same unsaturated acyclic carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
- C07C255/09—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton containing at least two cyano groups bound to the carbon skeleton
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—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"
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- 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"
- G01N2021/6432—Quenching
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Abstract
The preparation method of the invention discloses a kind of Salen ligand with cis-trans isomerism and its in Cu2+Application in probe and pH probe.Highly sensitive, highly selective cis- Salen ligand (CN-Z) and trans- Salen ligand (CN-E) are prepared using diaminomaleonitrile and 4- diethylin salicylide as raw material, and isomerization can occur for the two.Wherein, the Salen ligand with cis-trans isomerism is in Cu2+In the application of probe, with color, the variation and fluorescent quenching of ultraviolet-visible absorption spectroscopy, and detection limit is lower, Salen ligand with cis-trans isomerism has multiple pH response group and response range is wide, compared with the prior art, preparation method of the present invention is simple, at low cost, high income and in Cu2+Large-scale instrument is not needed in the application of probe and pH probe, it, can quick, easy, accurate recognition detection result by naked eye or fluorescence spectrum.
Description
Technical field
The invention belongs to analytical chemistry fields, more particularly, to a kind of preparation side of Salen ligand with cis-trans isomerism
Method and its in Cu2+Application in probe and pH probe.
Background technique
Cis-trans-isomer is widely present in nature, for general cis-trans-isomer, is all existed photochromic
Mechanism and electrochromism mechanism, the design feature of Salen ligand determine that it, with good optical property, under certain condition may be used
With with various metals ion carry out chelating ligands, these ligands and complexes spatial chemistry, structure, alloisomerism, magnetics,
Spectroscopy, Coordinative Chemistry, catalysis, analytical chemistry, photography, electric light shows, agricultural and the fields such as photochromic suffer from it is important
Effect, some Salen ligands have been successfully applied to the fluorescence detection field of metal ion.
Application of the fluorescence probe in biological field causes the great interest of people, and the Salen with cis-trans isomerism matches
Body is a kind of couple of Cu2+With highly selective, highly sensitive fluorescence probe, make it have as Cu2+Fluorescent quenching type probe
The possibility being applied in biosystem is expected to be applied to environmental monitoring and field of biological detection.
Most optical pH value probe can accurately detect pH value to a very small extent, can be widely applied to
Much aspects still sometimes detect pH in wider range and are also necessary, and how to design a kind of quick, simplicity
The probe of detection wider pH value range is of great significance.
Summary of the invention
It is an object of the invention to prepare a kind of highly sensitive, the highly selective Salen with cis-trans isomerism to match
Body, and its in Cu2+Application in probe and pH probe.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of preparation method of the Salen ligand with cis-trans isomerism, it is characterised in that: including cis- diamino maleic
The preparation method of two nitrilic type Salen ligands (CN-Z) and trans- diaminomaleonitrile type Salen ligand (CN-E), wherein
The structural formula of CN-Z are as follows:
The structural formula of CN-E are as follows:
It is described CN-Z's the preparation method is as follows:
(1) diaminomaleonitrile of 80~130mg and the 4- of 300~500mg are added in 250mL round-bottomed flask
Then the dehydrated alcohol of 70~120mL is added in diethylin salicylide, 0.03~0.1ml concentrated sulfuric acid is finally added dropwise and is catalyzed
Agent；
(2) 20~30h of reaction is stirred at room temperature, by filtering, obtains dark green solid；
(3) it is used washed with ether 3~5 times again after then rinsing dark green solid 3~5 times, 3 hours with ethyl alcohol；
(4) solvent finally is made with methylene chloride, is further purified by column chromatography.
It is described CN-E's the preparation method is as follows:
(1) diaminomaleonitrile of 80~130mg and the 4- of 300~500mg are added in 250mL round-bottomed flask
Then the dehydrated alcohol of 70~120mL is added in diethylin salicylide, 0.03~0.1ml concentrated sulfuric acid is finally added dropwise and makees catalyst；
(2) it is stirred to react 15 at 70 DEG C~90 DEG C~for 24 hours, by filtering, obtain darkviolet solid；
(3) it is used washed with ether 3~5 times again after then rinsing darkviolet solid 3~5 times, 3 hours with ethyl alcohol；
(4) solvent finally is made with the mixture of methylene chloride and ethyl acetate, is further purified by column chromatography.
Further, operation all in the preparation method of the CN-Z is completed under light protected environment.
Further, in the preparation method of the CN-E in step (4) mixture of methylene chloride and ethyl acetate ratio
Example is 2:1~5:1.
Further, the CN-Z and CN-E issues raw isomerization in the ultraviolet light irradiation of 365nm, at room temperature, irradiation
Ultravioletvisible absorption detection and fluorescence detection, isomery are carried out after 5min, 10min, 20min, 30min, 40min, 60min, 80min
Change process needs 30~50min can be completed.
In addition, the Salen- ligand with cis-trans isomerism is in Cu2+Application in probe and pH probe.
Wherein, the CN-Z is to Cu2+With coordination, stable four are formed with tooth copper complex, meanwhile, along with
The variation of color, the variation of ultraviolet-visible absorption spectroscopy and fluorescent quenching.
Further, Cu is added in the CN-E solution2+Afterwards, CN-E generation hydrolysis generates corresponding aldehyde and amine two
Kind presoma, meanwhile, along with the variation of color, the variation of ultraviolet-visible absorption spectroscopy and fluorescent quenching.
Further, the CN-Z is to Cu2+Fluorescence detection is done, detection is limited to 6.0nmol dm-3(0.39 ppb)。
Further, there are the CN-Z and CN-E multiple pH to respond group (C=N ,-OH ,-N (CH2CH3)2), and ring
Answering range is 1~14.
Further, the Salen ligand with cis-trans isomerism realizes test paper detection Cu2+And pH value.
Compared with prior art, the present invention using the above scheme has substantive distinguishing features and conspicuousness progress, specifically
It says, the invention has the following beneficial effects:
1) present invention prepares a kind of highly sensitive, highly selective Salen ligand with cis-trans isomerism, and the preparation
Method is simple, at low cost and high income；
2) fluorescence detection method high sensitivity provided by the invention, selectivity are good, detection limit is low, in Cu2+The application of probe
Middle generation fluorescent quenching, being capable of efficient, accurate detection Cu2+；
3) present invention is in Cu2+Application in probe does not need large-scale instrument, can be fast by naked eye or fluorescence spectrum
Speed, simplicity, accurate recognition detection result；
4) application of the present invention in pH probe realizes a kind of real-time, quick, easy, accurate detection wider pH value
Range；
Detailed description of the invention
Fig. 1 is the structural formula of CN-Z in the present embodiment；
Fig. 2 is the structural formula of CN-E in the present embodiment；
Fig. 3 is CN-Z and CN-E ultraviolet-visible absorption spectroscopy figure and fluorescence emission spectrogram of compound in the present embodiment；
Fig. 4 is CN-Z in the present embodiment to different equivalent proportion Cu2+The ultraviolet-visible absorption spectroscopy figure of identification；
Fig. 5 is CN-Z in the present embodiment to different equivalent proportion Cu2+The fluorescence emission spectrogram of compound of identification；
Fig. 6 is CN-E in the present embodiment to the ultraviolet-visible absorption spectroscopy figure of different metal ions；
Fig. 7 is the acetonitrile solution (1.0 × 10 of CN-E in the present embodiment-5mol dm-3) a drop Cu is added in2+Aqueous solution
Instantaneous photo；
Fig. 8 is CN-E in the present embodiment to the fluorescence emission spectrogram of compound of different metal ions；
Fig. 9 is CN-E in the present embodiment to the ultraviolet-visible absorption spectroscopy figure of different metal ions；
Figure 10 is CN-E in the present embodiment to the Cu of various concentration2+The fluorescence kinetic profiles of detection；
Figure 11 be the present embodiment in CN-E different pH value identifys photo (above: fluorescent lamp, below: 360nmUV- purple
Outer lamp)；
Figure 12 is the ultraviolet-visible absorption spectroscopy figure that CN-E identifies different pH value in the present embodiment；
Figure 13 is CN-E in the present embodiment to the titration curve (λ abs=564nm, λ em=610nm) of different pH；
Figure 14 is the Salen ligand with cis-trans isomerism of the present embodiment to Cu2+It is (left with the color change of the test paper of pH value
While being the photo under fluorescent lamp, the right is the photo under ultraviolet lamp).
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that the described embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiments shall fall within the protection scope of the present invention.
Embodiment 1: the preparation method of the Salen ligand with cis-trans isomerism
A kind of Salen ligand with cis-trans isomerism, including cis- diaminomaleonitrile type Salen ligand (CN-
Z) and trans- diaminomaleonitrile type Salen ligand (CN-E), wherein the structural formula of CN-Z as shown in Figure 1, CN-E knot
Structure formula is as shown in Figure 2.
CN-Z's the preparation method is as follows:
(1) diaminomaleonitrile of 108mg and the 4- diethylin water of 405mg are added in 250mL round-bottomed flask
Then the dehydrated alcohol of 100mL is added in poplar aldehyde, the 0.05ml concentrated sulfuric acid is finally added dropwise and makees catalyst；
(2) reaction is stirred at room temperature for 24 hours, by filtering, obtains dark green solid；
(3) it is used washed with ether 3 times again after then rinsing dark green solid 3 times, 3 hours with ethyl alcohol；
(4) solvent finally is made with methylene chloride, is further purified by column chromatography.
Above-mentioned all operations are completed under light protected environment, yield 32%.1H NMR(CDCl3) 1.2 1(t,
12H),3.39-3.45(q,8H),6.16(d,2H),6.3(dd,2H),7.19(d,2H),8.34(s,2H), 12.29(s,
2H)；Anal.Calcd(found):C,68.10(67.91)；H,6.59(6.87)；N,18.34 (18.17)；EI-MS,m/z
458。
CN-E's the preparation method is as follows:
(1) diaminomaleonitrile of 108mg and the 4- diethylin water of 405mg are added in 250mL round-bottomed flask
Then the dehydrated alcohol of 100mL is added in poplar aldehyde, the 0.05ml concentrated sulfuric acid is finally added dropwise and makees catalyst；
(2) it is stirred to react 19h at 79 DEG C, by filtering, obtains darkviolet solid；
(3) it is used washed with ether 3 times again after then rinsing darkviolet solid 3 times, 3 hours with ethyl alcohol；
(4) mixture (ratio of the mixture of methylene chloride and ethyl acetate of methylene chloride and ethyl acetate is finally used
Solvent is made for 3:1), is further purified by column chromatography.
Yield is 12%.1H NMR:(CDCl3)1.21(t,12H),6.16(d,2H),6.3
(dd,2H),7.19(d,2H),8.34(s,2H),11.75(s,2H).EI-MS,m/z458。
Embodiment 2: the Salen ligand with cis-trans isomerism is in Cu2+Application in probe
1) fluorescence analysis:
As shown in figure 3, can be seen that from ultraviolet-visible absorption spectroscopy of the CN-Z in acetonitrile solution and fluorescence emission spectrum
The maximum absorption band and maximum emission peak of CN-Z can be very good to apply the identification in metal ion, add in red light region
Enter the Cu of two equivalents2+Afterwards, apparent variation has occurred in the color of CN-Z solution, becomes brown from red, can be by visually seeing
It arrives；Such as Fig. 4, it can also be seen by ultraviolet-visible absorption spectroscopy, the maximum absorption band of CN-Z joined Cu at 565nm2+
Later, maximum absorption band red shift is to 590nm；As shown in figure 5, CN-Z is to Cu2+With coordination, due to Cu2+With paramagnetic
Property, CN-Z and Cu2+It forms stable four and fluorescent quenching occurs with tooth copper complex, therefore can be used for Cu with CN-Z2+It visits
Needle.
Cu is added in CN-E solution2+When, not only significant change occurs for ultraviolet-visible absorption spectroscopy, and passes through meat
Eye is it is seen that the color change become apparent, as shown in fig. 6, when other metal ions are added, the UV, visible light of CN-E
Absorption spectrum occur slight red shift, adjoint color change be from pink to purple, but be added Cu2+When, the purple of CN-E
Outer visible absorption spectra does not have absorption peak in visibility region, and variation sharply has occurred in solution colour, becomes from pink
Light yellow or even colourless, identification process can be completed in moment, as shown in fig. 7, the reason of causing this phenomenon is in the molten of CN-E
Cu is added in liquid2+Cu has occurred2+The hydrolytic process of the schiff bases of promotion.
Such as Fig. 8, the different metal ions (Li of two equivalents is added in CN-E solution+、K+、Mg2+、Hg2+、 Fe3+、Co2+、
Mn2+、Pb2+、Al3+、Ni2+、Ca2+、Zn2+、Cr3+、Cd2+、Ag+And Cu2+), fluorescence detection is carried out at identical conditions,
Under the ultraviolet lamp excitation of 365nm wavelength, it is added after different metal ions, most of metal ion makes the fluorescence intensity of CN-E
Slightly decline (Al3+、Mg2+、Ca2+、 Zn2+Deng), but only Cu2+The fluorescence of CN-E is quenched almost, so, CN-E can
Using the Cu as fluorescent quenching type2+Probe.
2) selectivity:
In order to measure CN-E selectivity, we have selected 18 metal ion species and Cu2+, fluorescence emission spectrum and UV, visible light
Absorption spectrum is as shown in Figure 8 and Figure 9, only addition Cu2+Afterwards, there is apparent selectivity.
3) sensitivity:
Such as Figure 10, the Cu of fluorescence intensity and various concentration2+(0~1.0 × 10-6mol dm-3) it is in good linear relationship,
Linear coefficient reaches 0.994 (n=10).Definition (CDL=3Sb/m) according to IUPAC to detection limit, passes through 10 blank solutions
Calculated detection limit reaches 6.0nmol dm-3(0.39ppb), therefore CN-E can be used as highly selective Cu2+Fluorescence
Probe.
CN-E has very strong fluorescence in 610nm, and 1 equivalent and 4 equivalent Cu are being added2+Afterwards, fluorescent quenching 96% and 100%,
(I0-I)/I0(emission peak at selection 610nm) is to Cu2+Concentration is in good linear relationship, related coefficient 0.996, with ten
A blank sample is reference, and detection is limited to 4.9ppb.
Embodiment 3: application of the Salen ligand with cis-trans isomerism in pH probe
CN-Z and CN-E is demonstrated by similar response to different pH value, select CN-E as identification pH probe example,
As shown in Figure 11, Figure 12, Figure 13, the ultraviolet-visible absorption spectroscopy and fluorescence emission spectrum of CN-E is stablized in a wider pH value
In range, pH value is 6~9, shows its potential application in terms of cytoplasm imaging；Even if in lower pH value range
It is interior, one pH probe can still act as by colorimetric detection from pH value for 2.5~5.0, CN-E, therefore, CN-E is in full pH
(1~14) is demonstrated by color change within the scope of value, not only in terms of ratio formula measurement and in terms of quick naked eyes identification
It is all very useful.
If Figure 14 is that have the Salen ligand of cis-trans isomerism to Cu2+With the color change of the pH test paper of pH value, examination is realized
Paper detects Cu2+And pH value.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (9)
1. a kind of preparation method of the Salen ligand with cis-trans isomerism, it is characterised in that: including cis- diamino maleic two
The preparation of nitrilic type Salen ligand (CN-Z) and trans- diaminomaleonitrile type Salen ligand (CN-E), wherein
The structural formula of CN-Z are as follows:
The structural formula of CN-E are as follows:
It is described CN-Z's the preparation method is as follows:
(1) diaminomaleonitrile of 80 ~ 130mg and the 4- diethylin of 300 ~ 500mg are added in 250mL round-bottomed flask
Then the dehydrated alcohol of 70 ~ 120mL is added in salicylide, 0.03 ~ 0.1ml concentrated sulfuric acid is finally added dropwise and makees catalyst；
(2) 20 ~ 30h of reaction is stirred at room temperature, by filtering, obtains dark green solid；
(3) it is used washed with ether 3 ~ 5 times again after then rinsing dark green solid 3 ~ 5 times, 3 hours with ethyl alcohol；
(4) solvent finally is made with methylene chloride, is further purified by column chromatography.
It is described CN-E's the preparation method is as follows:
(1) diaminomaleonitrile of 80 ~ 130mg and the 4- diethylin of 300 ~ 500mg are added in 250mL round-bottomed flask
Then the dehydrated alcohol of 70 ~ 120mL is added in salicylide, 0.03 ~ 0.1ml concentrated sulfuric acid is finally added dropwise and makees catalyst；
(2) it is stirred to react 15 at 70 DEG C ~ 90 DEG C ~ for 24 hours, by filtering, obtain darkviolet solid；
(3) it is used washed with ether 3 ~ 5 times again after then rinsing darkviolet solid 3 ~ 5 times, 3 hours with ethyl alcohol；
(4) solvent finally is made with the mixture of methylene chloride and ethyl acetate, is further purified by column chromatography.
2. the preparation method of the Salen ligand with cis-trans isomerism as described in claim 1, it is characterised in that: the CN-Z's
All operations are completed under light protected environment in preparation method.
3. the preparation method of the Salen ligand with cis-trans isomerism as described in claim 1, it is characterised in that: the CN-E's
The ratio of the mixture of methylene chloride and ethyl acetate is 2:1 ~ 5:1 in step (4) in preparation method.
4. as described in claim 1 with cis-trans isomerism Salen ligand preparation method, it is characterised in that: the CN-Z with
CN-E issues raw isomerization in the ultraviolet light irradiation of 365nm, and at room temperature, isomerization can be completed in 30 ~ 50min of irradiation.
5. a kind of Salen ligand with cis-trans isomerism is in Cu2+Application in probe and pH probe, which is characterized in that including power
Benefit requires 1 ~ 4 any Salen ligand (CN-Z and/or CN-E) with cis-trans isomerism.
6. the Salen ligand with cis-trans isomerism is in Cu as claimed in claim 52+Application in probe, which is characterized in that described
CN-Z is to Cu2+With coordination, stable four are formed with tooth copper complex, meanwhile, along with the variation of color, UV, visible light
The variation and fluorescent quenching of absorption spectrum.
Cu is added in the CN-E solution2+Afterwards, CN-E generation hydrolysis generates two kinds of presomas of corresponding aldehyde and amine, together
When, along with the variation of color, the variation of ultraviolet-visible absorption spectroscopy and fluorescent quenching.
7. the Salen ligand with cis-trans isomerism is in Cu as claimed in claim 52+Application in probe, which is characterized in that described
CN-Z is to Cu2+Fluorescence detection, detection are limited to 6.0 nmol dm−3 (0.39 ppb)。
8. application of the Salen ligand with cis-trans isomerism in pH probe as claimed in claim 5, which is characterized in that CN-Z
With CN-E there are multiple pH to respond group (C=N ,-OH ,-N(CH2CH3)2), and response range is 1 ~ 14.
9. the Salen ligand with cis-trans isomerism is in Cu as claimed in claim 52+Application in probe and pH probe, feature
It is, the Salen ligand with cis-trans isomerism realizes test paper detection Cu2+And pH value.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110172337A (en) * | 2019-05-30 | 2019-08-27 | 南京师范大学 | A kind of benzothiazole derivant fluorescence probe and its preparation method and application |
| CN111690145A (en) * | 2020-05-14 | 2020-09-22 | 遵义医科大学 | Pyridine type chiral Cu (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof |
| CN114894755A (en) * | 2022-04-25 | 2022-08-12 | 宜宾天原科创设计有限公司 | Qualitative analysis method of isopropyl hydrazine in ketazine hydrazine hydrate production system |
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2018
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| JINGHUI CHENG等: "Colorimetric and fluorescent pH and Cu2+ probes induced by photoisomerization of a maleonitrile-based Salen ligand", 《CHEM.COMMUN.》 * |
| JINGHUI CHENG等: "Optical Chemosensors Based on Transmetalation of Salen-Based Schiff Base Complexes", 《INORG.CHEM.》 * |
| JINGHUI CHENG等: "Synthesis and Photophysical Properties of Colorful Salen-Type Schiff Bases", 《J.PHYS.CHEM.》 * |
| 程景惠，向海峰: "具有二氨基顺丁烯二腈希夫碱作为比色和荧光pH探针和Cu2+探针", 《第十八届全国金属有机化学学术研讨会论文摘要集》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110172337A (en) * | 2019-05-30 | 2019-08-27 | 南京师范大学 | A kind of benzothiazole derivant fluorescence probe and its preparation method and application |
| CN110172337B (en) * | 2019-05-30 | 2022-09-13 | 南京师范大学 | Benzothiazole derivative fluorescent probe and preparation method and application thereof |
| CN111690145A (en) * | 2020-05-14 | 2020-09-22 | 遵义医科大学 | Pyridine type chiral Cu (II) -Salen ligand metal organic framework crystal material and preparation method and application thereof |
| CN114894755A (en) * | 2022-04-25 | 2022-08-12 | 宜宾天原科创设计有限公司 | Qualitative analysis method of isopropyl hydrazine in ketazine hydrazine hydrate production system |
| CN114894755B (en) * | 2022-04-25 | 2024-04-26 | 宜宾天原科创设计有限公司 | Qualitative analysis method of isopropyl hydrazine in ketazine hydrazine hydrate production system |
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