CN104371709A - Fluorescent sensing material as well as preparation method and application thereof - Google Patents
Fluorescent sensing material as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of chemical sensing materials and particularly relates to a fluorescent sensing material and a preparation method and application thereof. The fluorescent sensing material has a structure shown in a formula (I), wherein R1, R2 and R3 are independently selected from hydrogen, alkyl or alkoxy. The fluorescent sensing material provided by the invention can better form a coordination compound with zero valent palladium and divalent palladium in a solution, so that the fluorescent sensing material is in fluorescence quenching, thereby achieving the purpose of detecting zero valent palladium and divalent palladium. In addition, the fluorescent sensing material is not interfered by other metal ions such as mercury ions and platinum ions in the process of forming the coordination compound with palladium, so that the fluorescent sensing material has high selectivity on palladium. Experimental results show that the fluorescent sensing material provided by the invention has very high selectivity and anti-interference performance on detection of zero valent palladium and divalent palladium. The formula is as shown in the specification.
Description
Technical field
The invention belongs to chemical sensing material field, particularly relate to a kind of fluorescent sensing material and its preparation method and application.
Background technology
Along with development that is industrial, agriculture and urbanization process, the application of heavy metal (HMs) in agricultural, chemical industrie field is also in continuous expansion.As the one in heavy metal, palladium all plays important role in electronic industry, automotive industry, jewellery industry and chemical catalysis field, but simultaneously in product the residue problem of palladium also day by day annoying people, threaten human health.Research shows, the amino acid of palladium class material and sulfur-bearing, protein, DNA and other biomolecules have good complex ability, become second largest the metal carcinogens, particularly Palladous chloride that are only second to nickel, have very strong pungency to the eyes of people and skin.Therefore, for palladium class material, the especially focus be detected as in order to investigators study of zeroth order palladium and divalent palladium.
The method of traditional detection palladium has atomic absorption spectrometry (AAS), inductively coupled plasma atomic emission spectrometry (ICP-AES), solid-phase microextraction-high performance liquid chromatography (SPME-HPLC) and x-ray fluorescence method (XRF) etc.Although these methods can be analyzed the existence of palladium class material fast and have high sensitivity, they need complicated sample pretreatment process, strict experiment condition, costliness and complicated instrument and veteran operator usually.Therefore, have cheap, simple to operate, high sensitivity and optionally fluorescence sense technology more and more by the attention of people.This technology can detect ion delicately by utilizing emitted light color and Strength Changes.The exploitation of the fluorescent sensing material with excellent detection perform is received much concern.
Although the fluorescent sensing material detected for palladium of more existing excellent propertys is developed, the existing fluorescent sensing material detected for palladium detects the detection for zeroth order palladium or divalent palladium that only can be independent, can not detect zeroth order palladium and divalent palladium simultaneously.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of fluorescent sensing material and its preparation method and application, fluorescent sensing material provided by the invention can detect zeroth order palladium and divalent palladium simultaneously.
The invention provides a kind of fluorescent sensing material, there is formula (I) structure:
Wherein, R
1, R
2and R
3independently selected from hydrogen, alkyl or alkoxyl group.
Preferably, described R
1, R
2and R
3independently selected from hydrogen, C
1~ C
10alkyl or C
1~ C
10alkoxyl group.
Preferably, described R
1, R
2and R
3identical.
The invention provides a kind of preparation method of fluorescent sensing material, comprise the following steps:
A), mono-cyclic aromatic aldehyde, 2-cyanopyridine and ammonium salt mix in a solvent, and the mixture be mixed to get heats, and obtains the fluorescent sensing material of structure shown in formula (I);
Wherein, R
1, R
2and R
3independently selected from hydrogen, alkyl or alkoxyl group;
Described mono-cyclic aromatic aldehyde is phenyl aldehyde, to one or more in alkylbenzaldehyde and p-alkoxybenzaldehydes.
Preferably, described mono-cyclic aromatic aldehyde be phenyl aldehyde, to alkylbenzaldehyde or p-alkoxybenzaldehydes.
Preferably, described ammonium salt is one or more in ammonium acetate, ammonium chloride, ammonium nitrate, ammonium sulfate and volatile salt.
Preferably, the mol ratio of described 2-cyanopyridine, mono-cyclic aromatic aldehyde and ammonium salt is 1:1 ~ 4:2 ~ 6.
Preferably, the temperature of described heating is 70 ~ 120 DEG C.
Preferably, the mode of described heating is microwave exposure.
The invention provides a kind of detection method of palladium class material, comprise the following steps:
By fluorescent sensing material mentioned above, testing sample and solvent, detect the fluorescence intensity of gained mixture;
By described fluorescent sensing material and described solvent, detect the fluorescence intensity of gained solution;
If the fluorescence intensity of gained mixture is lower than the fluorescence intensity of gained solution, then contain zeroth order palladium and/or divalent palladium in described testing sample, otherwise not containing zeroth order palladium and/or divalent palladium in described testing sample.
Compared with prior art, the invention provides a kind of fluorescent sensing material and its preparation method and application.Fluorescent sensing material provided by the invention, has formula (I) structure, wherein, and R
1, R
2and R
3independently selected from hydrogen, alkyl or alkoxyl group.Fluorescent sensing material provided by the invention can well form coordination compound, thus make this fluorescent sensing material quenching of fluorescence with zeroth order palladium, divalent palladium in the solution, reaches the object detecting zeroth order palladium and divalent palladium.In addition, this fluorescent sensing material can not be subject to other the metal ion disturbance such as mercury ion, platinum ion being formed in coordination compound process with palladium, has very high selectivity to palladium.Experimental result shows, the detection of fluorescent sensing material provided by the invention to zeroth order palladium and divalent palladium has very high selectivity and freedom from jamming.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to the accompanying drawing provided.
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the fluorescent sensing material that the embodiment of the present invention 1 obtains;
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the fluorescent sensing material that the embodiment of the present invention 2 obtains;
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of the fluorescent sensing material that the embodiment of the present invention 3 obtains;
Fig. 4 is the fluorescent emission intensity histogram of fluorescent sensing material in different solutions that the embodiment of the present invention 1 obtains;
Fig. 5 is the fluorescent emission intensity histogram of fluorescent sensing material in different solutions that the embodiment of the present invention 2 obtains;
Fig. 6 is the fluorescent emission intensity histogram of fluorescent sensing material in different solutions that the embodiment of the present invention 3 obtains;
Fig. 7 is the uv-absorbing of the obtained fluorescent sensing material of the embodiment of the present invention 1 in different solvents and fluorescent emission spectrogram;
Fig. 8 is that the obtained fluorescent sensing material of the embodiment of the present invention 1 is at different Pd
2+fluorescent emission spectrogram in the acetonitrile solution of concentration;
Fig. 9 is the obtained fluorescent sensing material of the embodiment of the present invention 1 and Pd
2+job ' s plot curve;
Figure 10 is the obtained fluorescent sensing material of the embodiment of the present invention 1 and the uv absorption spectra of different metal ion in acetonitrile;
Figure 11 is the obtained fluorescent sensing material of the embodiment of the present invention 1 and the fluorescent emission spectrogram of different metal ion in acetonitrile;
Figure 12 is the obtained fluorescent sensing material of the embodiment of the present invention 1 and the Fluorescence Increasing multiple figure of different metal ion in acetonitrile;
Figure 13 is fluorescent sensing material fluorescent emission intensity histogram in the solution containing different palladium material that the embodiment of the present invention 1 obtains;
Figure 14 is the variation diagram of the obtained fluorescent sensing material of the embodiment of the present invention 1 and the fluorescent emission intensity of different metal ion in acetonitrile;
Figure 15 is the obtained fluorescent sensing material of the embodiment of the present invention 2 and the uv absorption spectra of different metal ion in acetonitrile;
Figure 16 is the obtained fluorescent sensing material of the embodiment of the present invention 2 and the fluorescent emission spectrogram of different metal ion in acetonitrile;
Figure 17 is fluorescent sensing material fluorescent emission intensity histogram in the solution containing different palladium material that the embodiment of the present invention 2 obtains;
Figure 18 is the obtained fluorescent sensing material of the embodiment of the present invention 3 and the uv absorption spectra of different metal ion in acetonitrile;
Figure 19 is the obtained fluorescent sensing material of the embodiment of the present invention 3 and the fluorescent emission spectrogram of different metal ion in acetonitrile;
Figure 20 is fluorescent sensing material fluorescent emission intensity histogram in the solution containing different palladium material that the embodiment of the present invention 3 obtains.
Embodiment
Be clearly and completely described to the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of fluorescent sensing material, there is formula (I) structure:
Wherein, R
1, R
2and R
3independently be selected from hydrogen, alkyl or alkoxyl group.
Fluorescent sensing material provided by the invention has formula (I) structure.Wherein, R
1, R
2and R
3independently selected from hydrogen, alkyl or alkoxyl group, preferably from hydrogen, C
1~ C
10alkyl or C
1~ C
10alkoxyl group, more preferably from hydrogen, C
1~ C
5alkyl or C
1~ C
5alkoxyl group, most preferably from hydrogen, methyl or methoxy.In certain embodiments of the present invention, described R
1, R
2and R
3preferably identical.
In the present invention, described fluorescent sensing material is specifically as follows the one in structural compounds shown in formula (II), formula (III) and formula (IV):
Fluorescent sensing material provided by the invention can well form coordination compound, thus make this fluorescent sensing material quenching of fluorescence with zeroth order palladium, divalent palladium in the solution, reaches the object detecting zeroth order palladium and divalent palladium.In addition, this fluorescent sensing material can not be subject to other the metal ion disturbance such as mercury ion, platinum ion being formed in coordination compound process with palladium, has very high selectivity to palladium.
The invention provides a kind of preparation method of fluorescent sensing material, comprise the following steps:
A), mono-cyclic aromatic aldehyde, 2-cyanopyridine and ammonium salt mix in a solvent, and the mixture be mixed to get heats, and obtains the fluorescent sensing material of structure shown in formula (I);
Wherein, R
1, R
2and R
3independently selected from hydrogen, alkyl or alkoxyl group;
Described mono-cyclic aromatic aldehyde is phenyl aldehyde, to one or more in alkylbenzaldehyde and p-alkoxybenzaldehydes.
In the preparation method provided of the present invention, first mono-cyclic aromatic aldehyde, 2-cyanopyridine and ammonium salt are mixed in a solvent.Wherein, described mono-cyclic aromatic aldehyde is phenyl aldehyde, to one or more in alkylbenzaldehyde and p-alkoxybenzaldehydes, is preferably phenyl aldehyde, to alkylbenzaldehyde or p-alkoxybenzaldehydes.Described to alkylbenzaldehyde be preferably p-tolyl aldehyde, p-ethylbenzaldehyde, to propylbenzaldehyde, to butyl benzaldehyde, to amylbenzene formaldehyde, to hexylbenzaldehyde, to heptyl benzene formaldehyde, to octyl group phenyl aldehyde, to nonyl benzene formaldehyde or to decyl phenyl aldehyde.Described p-alkoxybenzaldehydes be preferably aubepine, p-ethoxybenzaldehyde, to propoxybenzaldehyde, to butoxybenzaldehyde, to pentyloxybenzaldehyde, to hexyloxybenzaldehyde, to heptyloxybenzaldehyde, to octyloxybenzaldehyde, to oxygen benzaldehyde or to oxygen benzaldehyde in the last of the ten Heavenly stems in the ninth of the ten Heavenly Stems.Described solvent is preferably dimethyl fumarate.Described ammonium salt be preferably in ammonium acetate, ammonium chloride, ammonium nitrate, ammonium sulfate and volatile salt one or more.The mol ratio of described 2-cyanopyridine, mono-cyclic aromatic aldehyde and ammonium salt is preferably 1:1 ~ 4:2 ~ 6, is more preferably 1:2.5:4.
After mono-cyclic aromatic aldehyde, 2-cyanopyridine and ammonium salt mix in a solvent, the mixture be mixed to get is heated.The temperature of described heating is preferably 70 ~ 120 DEG C.The mode of described heating can be oil bath, also can be microwave exposure, be preferably microwave exposure.In the present invention, when type of heating is oil bath, the time of heating is preferably 7 ~ 8h; When type of heating is microwave exposure, the time of heating is preferably 10 ~ 60min.
After heating terminates, in the reaction system of mono-cyclic aromatic aldehyde, 2-cyanopyridine, ammonium salt and solvent composition, add water, cancellation is reacted, and obtains reaction product solution.Described reaction product solution carries out aftertreatment, obtains the fluorescent sensing material of structure shown in formula (I).The concrete mode of described aftertreatment is preferably: described reaction product solution passes through extraction, washing, drying successively, revolves steaming, column chromatography and recrystallization, obtains the fluorescent sensing material of structure shown in formula (I).The extraction agent of described extraction is preferably ethyl acetate; The washing composition of described washing is preferably saturated aqueous common salt; The siccative of described drying is preferably anhydrous sodium sulphate; The solvent of described recrystallization is preferably acetonitrile.
The present invention is with raw material cheap and easy to get, and in next step legal system of catalyst-free condition for fluorescent sensing material, step is simple, and processing ease, obtained fluorescent sensing material is the fluorescent sensing material that a class can detect the high sensitivity of zeroth order palladium and divalent palladium simultaneously.
The invention provides a kind of detection method of palladium class material, comprise the following steps:
By fluorescent sensing material mentioned above, testing sample and solvent, detect the fluorescence intensity of gained solution;
By described fluorescent sensing material and described solvent, detect the fluorescence intensity of gained solution;
If the fluorescence intensity of gained mixture is lower than the fluorescence intensity of gained solution, then contain zeroth order palladium and/or divalent palladium in described testing sample, otherwise not containing zeroth order palladium and/or divalent palladium in described testing sample.
In detection method provided by the invention, by fluorescent sensing material mentioned above, testing sample and solvent, after mixing, detect the fluorescence intensity of gained mixture.Described solvent is preferably acetonitrile.The amount ratio of described fluorescent sensing material and solvent is preferably 1 (mol): 10
3~ 10
5(L) 1 (mol): 10, are more preferably
4~ 10
5(L).
In the present invention, the mode of described fluorescent sensing material, testing sample and solvent is preferably: mixed with partial solvent by testing sample, obtain testing sample solution, fluorescent sensing material is mixed with partial solvent, obtain fluorescent sensing material solution, then by the solvent of the solution of described testing sample, the solution of fluorescent sensing material and surplus.
In an embodiment provided by the invention, described testing sample is palladium compounds, and described palladium compounds is PdCl
2, Pd (dba)
2, PdCl
2and Pd (OAc) (dppf)
2in one or more.In described testing sample solution, the molar content of palladium compounds is 10
-3~ 10
-4mol/L.In described fluorescent sensing material solution, the molar content of fluorescent sensing material is 10
-3~ 10
-4mol/L.In the mixture of the solvent gained of the solution of described testing sample, the solution of fluorescent sensing material and surplus, the mol ratio of palladium compounds and fluorescent sensing material is 0.1 ~ 5:1.
In another embodiment provided by the invention, described testing sample is made up of palladium compounds and other metallic compounds, and described palladium compounds is PdCl
2, Pd (dba)
2, PdCl
2and Pd (OAc) (dppf)
2in one or more, other metallic compounds described are one or more in platinum salt, mercury salt, zinc salt, pink salt, rubidium salt, lead salt, nickel salt, sodium salt, magnesium salts, lithium salts, sylvite, molysite, mantoquita, cobalt salt, cadmium salt, calcium salt and barium salt, and described platinum salt is PtCl
2, described mercury salt is HgCl
2, described zinc salt is ZnCl
2, described pink salt is SnCl
2, described rubidium salt is RuCl
3, described lead salt is PbCl
2, described nickel salt is NiCl
2, described sodium salt is NaCl, and described magnesium salts is MgCl
2, described lithium salts is LiCl, and described lithium salts is KCl, and described molysite is FeCl
3, described mantoquita is CuCl
2, described cobalt salt is CoCl
2, described cadmium salt is CdCl
2, described calcium salt is CaCl
2, described barium salt is BaCl
2.In described testing sample, the mol ratio of palladium compounds and other metallic compounds is 1 ~ 3:5 ~ 10.In described testing sample solution, the molar content of palladium compounds is 10
-3~ 10
-4mol/L.In described fluorescent sensing material solution, the molar content of fluorescent sensing material is 10
-3~ 10
-4mol/L.In the mixture of the solvent gained of the solution of described testing sample, the solution of fluorescent sensing material and surplus, the mol ratio content of palladium compounds and fluorescent sensing material is 0.1 ~ 5:1.
By described fluorescent sensing material and described solvent, after mixing, detect the fluorescence intensity of gained solution.The amount ratio of described fluorescent sensing material and described solvent and described fluorescent sensing material, testing sample are identical with the amount ratio of solvent with fluorescent sensing material described during solvent.The equipment of the present invention to fluorescence intensity is not particularly limited, and is preferably fluorescence spectrophotometer.
After obtaining the fluorescence intensity of described fluorescent sensing material, testing sample and solvent gained mixture and the fluorescence intensity of described fluorescent sensing material and solvent gained solution, both fluorescence intensity levels are compared, if the fluorescence intensity of gained mixture is lower than the fluorescence intensity of gained solution, then contain zeroth order palladium and/or divalent palladium in described testing sample, otherwise not containing zeroth order palladium and/or divalent palladium in described testing sample.
Detection method provided by the invention may be used for the detection of zeroth order palladium and divalent palladium.Experimental result shows, the detection accuracy of detection method provided by the invention to zeroth order palladium and divalent palladium is high.
For the purpose of clearer, be described in detail below by following examples.
Embodiment 1
0.265g phenyl aldehyde, 0.105g 2-cyanopyrimidine, 0.308g ammonium acetate and 2mL dimethyl formamide are added in 20mL microwave reaction pipe, reacts 30 minutes under 100 DEG C of microwave radiation conditions.After microwave radiation stops, solution becomes dark, adds 5mL water, obtain reaction product solution in microwave reaction pipe.
Reaction product solution is extracted with ethyl acetate (10mL × 3), extracts the organic phase that obtains successively through saturated common salt water washing, anhydrous sodium sulfate drying with revolve steaming, obtains crude product.Crude product through column chromatography for separation and recrystallized from acetonitrile, obtains fluorescent sensing material again.
The fluorescent sensing material obtained to the present embodiment carries out hydrogen nuclear magnetic resonance spectrum analysis, and result as shown in Figure 1.Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the fluorescent sensing material that the embodiment of the present invention 1 obtains.Hydrogen spectrum analysis result is as shown in Figure 1:
1h NMR (400MHz, DMSO) δ 8.33-8.31 (m, 2H), 7.65-7.62 (m, 3H), 7.41-7.38 (m, 4H), 7.36-7.30 (m, 7H).
The fluorescent sensing material obtained to the present embodiment carries out carbon-13 nmr spectra analysis, and result is:
13cNMR (101MHz, DMSO) δ 156.88,140.12,132.03,130.38,129.68,129.46,128.46,128.32,127.64.
From proton nmr spectra and carbon spectrum analysis result, the fluorescent sensing material that the present embodiment obtains has formula (I) structure, and R is hydrogen.
The fluorescent sensing material obtained to the present embodiment carries out purity check and calculation of yield, and result is: productive rate 51%, purity 98%.
Embodiment 2
0.300g p-tolyl aldehyde, 0.105g 2-cyanopyrimidine, 0.308g ammonium acetate and 2mL dimethyl formamide are added in 20mL microwave reaction pipe, reacts 30 minutes under 100 DEG C of microwave radiation conditions.After microwave radiation stops, solution becomes dark, adds 5mL water, obtain reaction product solution in microwave reaction pipe.
Reaction product solution is extracted with ethyl acetate (10mL × 3), extracts the organic phase that obtains successively through saturated common salt water washing, anhydrous sodium sulfate drying with revolve steaming, obtains crude product.Crude product through column chromatography for separation and recrystallized from acetonitrile, obtains fluorescent sensing material again.
The fluorescent sensing material obtained to the present embodiment carries out hydrogen nuclear magnetic resonance spectrum analysis, and result as shown in Figure 2.Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the fluorescent sensing material that the embodiment of the present invention 2 obtains.Hydrogen spectrum analysis result is as shown in Figure 2:
1h NMR (400MHz, DMSO) δ 13.91 (s, 1H), 8.20 (d, J=8.1Hz, 2H), 7.43 (d, J=8.1Hz, 2H), 7.28 (d, J=7.9Hz, 4H), 7.13 (d, J=7.9Hz, 4H), 2.42 (s, 3H), 2.31 (s, 6H).
The fluorescent sensing material obtained to the present embodiment carries out carbon-13 nmr spectra analysis, and result is:
13cNMR (101MHz, DMSO) δ 157.03,149.11,146.50,141.44,140.51,138.18,137.77,136.74,136.36,130.18,129.94,129.56,128.98,128.76,126.90,125.87,21.55,21.29,21.08.
From proton nmr spectra and carbon spectrum analysis result, the fluorescent sensing material that the present embodiment obtains has formula (I) structure, and R is methyl.
The fluorescent sensing material obtained to the present embodiment carries out purity check and calculation of yield, and result is: productive rate 30%, purity 98%.
Embodiment 3
0.340g aubepine, 0.105g 2-cyanopyrimidine, 0.308g ammonium acetate and 2mL dimethyl formamide are added in 20mL microwave reaction pipe, reacts 30 minutes under 100 DEG C of microwave radiation conditions.After microwave radiation stops, solution becomes dark, adds 5mL water, obtain reaction product solution in microwave reaction pipe.
Reaction product solution is extracted with ethyl acetate (10mL × 3), extracts the organic phase that obtains successively through saturated common salt water washing, anhydrous sodium sulfate drying with revolve steaming, obtains crude product.Crude product through column chromatography for separation and recrystallized from acetonitrile, obtains fluorescent sensing material again.
The fluorescent sensing material obtained to the present embodiment carries out hydrogen nuclear magnetic resonance spectrum analysis, and result as shown in Figure 3.Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of the fluorescent sensing material that the embodiment of the present invention 3 obtains.Hydrogen spectrum analysis result is as shown in Figure 3:
1h NMR (400MHz, CDCl
3) δ 12.79 (s, 1H), 7.78 (d, J=8.8Hz, 2H), 7.42 (d, J=6.6Hz, 2H), 7.32 (d, J=6.4Hz, 2H), 6.81 (d, J=6.5Hz, 2H), 6.69 (d, J=8.8Hz, 2H), 6.60 (d, J=6.5Hz, 2H), 3.80 (s, 6H), 3.65 (s, 3H).
The fluorescent sensing material obtained to the present embodiment carries out carbon-13 nmr spectra analysis, and result is:
13cNMR (101MHz, CDCl
3) δ 161.86,159.63,159.61,159.44,159.39,157.00,131.54,131.50,131.40,131.37,131.34,131.32,128.72,121.12,114.24,113.73,113.52,55.31,55.23,55.00.
From proton nmr spectra and carbon spectrum analysis result, the fluorescent sensing material that the present embodiment obtains has formula (I) structure, and R is methoxyl group.
The fluorescent sensing material obtained to the present embodiment carries out purity check and calculation of yield, and result is: productive rate 27%, purity 98%.
Embodiment 4
0.265g phenyl aldehyde, 0.105g 2-cyanopyrimidine, 0.308g ammonium acetate and 2mL dimethyl formamide are added in 20mL microwave reaction pipe, reacts 60 minutes under 70 DEG C of microwave radiation conditions.After microwave radiation stops, solution becomes dark, adds 5mL water, obtain reaction product solution in microwave reaction pipe.
Reaction product solution is extracted with ethyl acetate (10mL × 3), extracts the organic phase that obtains successively through saturated common salt water washing, anhydrous sodium sulfate drying with revolve steaming, obtains crude product.Crude product through column chromatography for separation and recrystallized from acetonitrile, obtains fluorescent sensing material again.
The fluorescent sensing material obtained to the present embodiment carries out hydrogen nuclear magnetic resonance spectrum analysis, and result is:
1hNMR (400MHz, DMSO) δ 8.33-8.31 (m, 2H), 7.65-7.62 (m, 3H), 7.41-7.38 (m, 4H), 7.36-7.30 (m, 7H).The fluorescent sensing material obtained to the present embodiment carries out carbon-13 nmr spectra analysis, and result is:
13c NMR (101MHz, DMSO) δ 156.88,140.12,132.03,130.38,129.68,129.46,128.46,128.32,127.64.From proton nmr spectra and carbon spectrum analysis result, the fluorescent sensing material that the present embodiment obtains has formula (I) structure, and R is hydrogen.
The fluorescent sensing material obtained to the present embodiment carries out purity check and calculation of yield, and result is: productive rate 43%, purity 98%.
Embodiment 5
0.300g p-tolyl aldehyde, 0.105g 2-cyanopyrimidine, 0.308g ammonium acetate and 2mL dimethyl formamide are added in 20mL microwave reaction pipe, reacts 10 minutes under 120 DEG C of microwave radiation conditions.After microwave radiation stops, solution becomes dark, adds 5mL water, obtain reaction product solution in microwave reaction pipe.
Reaction product solution is extracted with ethyl acetate (10mL × 3), extracts the organic phase that obtains successively through saturated common salt water washing, anhydrous sodium sulfate drying with revolve steaming, obtains crude product.Crude product through column chromatography for separation and recrystallized from acetonitrile, obtains fluorescent sensing material again.
The fluorescent sensing material obtained to the present embodiment carries out hydrogen nuclear magnetic resonance spectrum analysis, and result is:
1hNMR (400MHz, DMSO) δ 13.91 (s, 1H), 8.20 (d, J=8.1Hz, 2H), 7.43 (d, J=8.1Hz, 2H), 7.28 (d, J=7.9Hz, 4H), 7.13 (d, J=7.9Hz, 4H), 2.42 (s, 3H), 2.31 (s, 6H).The fluorescent sensing material obtained to the present embodiment carries out carbon-13 nmr spectra analysis, and result is:
13cNMR (101MHz, DMSO) δ 157.03,149.11,146.50,141.44,140.51,138.18,137.77,136.74,136.36,130.18,129.94,129.56,128.98,128.76,126.90,125.87,21.55,21.29,21.08.From proton nmr spectra and carbon spectrum analysis result, the fluorescent sensing material that the present embodiment obtains has formula (I) structure, and R is methyl.
The fluorescent sensing material obtained to the present embodiment carries out purity check and calculation of yield, and result is: productive rate 29%, purity 98%.
Embodiment 6
0.340g aubepine, 0.105g 2-cyanopyrimidine, 0.308g ammonium acetate and 2mL dimethyl formamide are added in 20mL reaction tubes, in 100 DEG C of oil baths, reacts 7h.After oil bath stops, solution becomes dark, adds 5mL water, obtain reaction product solution in microwave reaction pipe.
Reaction product solution is extracted with ethyl acetate (10mL × 3), extracts the organic phase that obtains successively through saturated common salt water washing, anhydrous sodium sulfate drying with revolve steaming, obtains crude product.Crude product through column chromatography for separation and recrystallized from acetonitrile, obtains fluorescent sensing material again.
The fluorescent sensing material obtained to the present embodiment carries out hydrogen nuclear magnetic resonance spectrum analysis, and result is:
1hNMR (400MHz, CDCl
3) δ 12.79 (s, 1H), 7.78 (d, J=8.8Hz, 2H), 7.42 (d, J=6.6Hz, 2H), 7.32 (d, J=6.4Hz, 2H), 6.81 (d, J=6.5Hz, 2H), 6.69 (d, J=8.8Hz, 2H), 6.60 (d, J=6.5Hz, 2H), 3.80 (s, 6H), 3.65 (s, 3H).The fluorescent sensing material obtained to the present embodiment carries out carbon-13 nmr spectra analysis, and result is:
13c NMR (101MHz, CDCl
3) δ 161.86,159.63,159.61,159.44,159.39,157.00,131.54,131.50,131.40,131.37,131.34,131.32,128.72,121.12,114.24,113.73,113.52,55.31,55.23,55.00.From proton nmr spectra and carbon spectrum analysis result, the fluorescent sensing material that the present embodiment obtains has formula (I) structure, and R is methoxyl group.
The fluorescent sensing material obtained to the present embodiment carries out purity check and calculation of yield, and result is: productive rate 22%, purity 98%.
Embodiment 7
Palladium class material test experience
By 10
-4fluorescent sensing material, 10mL acetonitrile and 5 × 10 that mmol embodiment 1 is obtained
-4mmolPdCl
2mixing, obtains detecting sample 1; By 10
-4fluorescent sensing material, 10mL acetonitrile and 5 × 10 that mmol embodiment 1 is obtained
-4mmol ZnCl
2mixing, obtains detecting sample 2; By 10
-4the fluorescent sensing material that mmol embodiment 1 is obtained and the mixing of 10mL acetonitrile, obtain reference sample.
Use fluorescence emission spectrometer to detect the fluorescent emission intensity of reference sample and detection sample respectively, result as shown in Figure 4.Fig. 4 is the obtained fluorescent emission intensity histogram of fluorescent sensing material in different solutions of the embodiment of the present invention 1, and in figure, A is reference sample, B is for detecting sample 1, C for detecting sample 2.
As seen in Figure 4, the fluorescent emission intensity of B is starkly lower than A, and the fluorescent emission intensity of C, higher than A, illustrates and detects containing zeroth order palladium or divalent palladium in sample 1, detects in sample 2 not containing palladium class material.Detected result conforms to practical situation, illustrates the detection method that the present embodiment provides accurately can detect in sample whether there is palladium class material.
Embodiment 8
Palladium class material test experience
By 10
-4fluorescent sensing material, 10mL acetonitrile and 5 × 10 that mmol embodiment 2 is obtained
-4mmolPd (dba)
2mixing, obtains detecting sample 1; By 10
-4fluorescent sensing material, 10mL acetonitrile and 5 × 10 that mmol embodiment 2 is obtained
-4mmol PbCl
2mixing, obtains detecting sample 2; By 10
-4the fluorescent sensing material that mmol embodiment 2 is obtained and the mixing of 10mL acetonitrile, obtain reference sample.
Use fluorescence emission spectrometer to detect the fluorescent emission intensity of reference sample and detection sample respectively, result as shown in Figure 5.Fig. 5 is the obtained fluorescent emission intensity histogram of fluorescent sensing material in different solutions of the embodiment of the present invention 2, and in figure, A is reference sample, B is for detecting sample 1, C for detecting sample 2.
As seen in Figure 5, the fluorescent emission intensity of B is starkly lower than A, and the fluorescent emission intensity of C, higher than A, illustrates and detects containing zeroth order palladium or divalent palladium in sample 1, detects in sample 2 not containing palladium class material.Detected result conforms to practical situation, illustrates the detection method that the present embodiment provides accurately can detect in sample whether there is palladium class material.
Embodiment 9
Palladium class material test experience
By 10
-4fluorescent sensing material, 10mL acetonitrile and 5 × 10 that mmol embodiment 3 is obtained
-4mmolPd (OAc)
2mixing, obtains detecting sample 1; By 10
-4fluorescent sensing material, 10mL acetonitrile and 5 × 10 that mmol embodiment 3 is obtained
-4mmol BaCl
2mixing, obtains detecting sample 2; By 10
-4the fluorescent sensing material that mmol embodiment 3 is obtained and the mixing of 10mL acetonitrile, obtain reference sample.
Use fluorescence emission spectrometer to detect the fluorescent emission intensity of reference sample and detection sample respectively, result as shown in Figure 6.Fig. 6 is the obtained fluorescent emission intensity histogram of fluorescent sensing material in different solutions of the embodiment of the present invention 3, and in figure, A is reference sample, B is for detecting sample 1, C for detecting sample 2.
As seen in Figure 6, the fluorescent emission intensity of B is starkly lower than A, and the fluorescent emission intensity of C, higher than A, illustrates and detects containing zeroth order palladium or divalent palladium in sample 1, detects in sample 2 not containing palladium class material.Detected result conforms to practical situation, illustrates the detection method that the present embodiment provides accurately can detect in sample whether there is palladium class material.
Embodiment 10
The impact of different solvents on fluorescent sensing material uv-absorbing intensity and fluorescent emission intensity is tested
Respectively by the methylene dichloride of 10mL, ethanol, acetonitrile, tetrahydrofuran (THF), toluene and 10
-4the fluorescent sensing material mixing that mmol embodiment 1 is obtained, detect its uv-absorbing intensity and fluorescent emission intensity, fluorescent emission excitation wavelength is 360nm, and result as shown in Figure 7.Fig. 7 is the uv-absorbing of the obtained fluorescent sensing material of the embodiment of the present invention 1 in different solvents and fluorescent emission spectrogram.
As seen in Figure 7, the uv-absorbing of the fluorescent sensing material that embodiment 1 is obtained in different solvents and fluorescence emission wavelengths scope do not have considerable change.The fluorescent sensing material that embodiment 1 obtains fluorescent emission intensity is in ethanol the strongest, and the fluorescent emission intensity in acetonitrile is the most weak.
Embodiment 11
Different Pd
2+concentration is tested the impact of fluorescent sensing material fluorescent emission intensity
Be 0,0.2 × 10 by concentration respectively
-5mol/L, 0.4 × 10
-5mol/L, 0.6 × 10
-5mol/L, 0.8 × 10
-5mol/L, 1 × 10
-5mol/L, 2 × 10
-5mol/L, 3 × 10
-5mol/L, 4 × 10
-5mol/L, 5 × 10
-5the PdCl of mol/L
2acetonitrile solution 10mL and 10
-4mmol embodiment 1 obtains fluorescent sensing material mixing, and detect its fluorescent emission intensity, fluorescent emission excitation wavelength is 360nm, and result as shown in Figure 8.Fig. 8 is that the obtained fluorescent sensing material of the embodiment of the present invention 1 is at different Pd
2+fluorescent emission spectrogram in the acetonitrile solution of concentration, in figure, 0 equivalent PdCl
2represent and detect in sample not containing PdCl
2, 5 equivalent PdCl
2represent and detect PdCl in sample
2concentration be 5 × 10
-5mol/L.
As seen in Figure 8, along with PdCl
2the increase of concentration, the fluorescence intensity of the fluorescent sensing material that embodiment 1 is obtained weakens gradually.
Embodiment 12
Fluorescent sensing material and Pd
2+in conjunction with the mensuration of ratio
Test specimens is prepared according to the proportioning in table 1.
Table 1Job ' s plot curve test specimens component proportion table
| Project | Fluorescent sensing material/mmol that embodiment 1 is obtained | PtCl 2/mmol | Acetonitrile/mL |
| 1 | 0 | 2.5×10 -4 | 10 |
| 2 | 0.25×10 -4 | 2.25×10 -4 | 10 |
| 3 | 0.5×10 -4 | 2.0×10 -4 | 10 |
| 4 | 0.75×10 -4 | 1.75×10 -4 | 10 |
| 5 | 1.0×10 -4 | 1.5×10 -4 | 10 |
| 6 | 1.25×10 -4 | 1.25×10 -4 | 10 |
| 7 | 1.5×10 -4 | 1.0×10 -4 | 10 |
| 8 | 1.75×10 -4 | 0.75×10 -4 | 10 |
| 9 | 2.0×10 -4 | 0.5×10 -4 | 10 |
| 10 | 2.25×10 -4 | 0.25×10 -4 | 10 |
| 11 | 2.5×10 -4 | 0 | 10 |
Detect the fluorescence sense intensity of 11 test specimens in table 1, and draw Job ' splot curve according to fluorescence sense intensity level.As shown in Figure 9, Fig. 9 is the obtained fluorescent sensing material of the embodiment of the present invention 1 and Pd to Job ' s plot curve
2+job ' s plot curve, wherein, X
pd=C
pd/ (C
pd+ C
l1), C
pdfor Pd in test specimens
2+volumetric molar concentration, C
l1for the volumetric molar concentration of the fluorescent sensing material that embodiment in test specimens 1 obtains; I
0it is the fluorescent emission intensity value of the first test specimens; I represents the fluorescent emission intensity value of test specimens.
As seen in Figure 9, the fluorescent sensing material that embodiment 1 is obtained and Pd
2+in conjunction with comparing for 1:1.
Embodiment 13
The impact experiment of the fluorescent sensing material uv-absorbing intensity that different metal ion pair embodiment 1 is obtained and fluorescent emission intensity
Respectively by 5 × 10
-4the PtCl of mmol
2, HgCl
2, ZnCl
2, SnCl
2, RuCl
3, PbCl
2, NiCl
2, NaCl, MgCl
2, LiCl, KCl, FeCl
3, CuCl
2, CoCl
2, CdCl
2, CaCl
2, BaCl
2with 10
-4the fluorescent sensing material that mmol embodiment 1 is obtained and the mixing of 10mL acetonitrile, obtain a series of detection sample; By 10
-4the fluorescent sensing material that mmol embodiment 1 is obtained and the mixing of 10mL acetonitrile, obtain reference sample.
Carry out the detection of uv-absorbing strength to above-mentioned obtained a series of detection samples, detected result as shown in Figure 10.Figure 10 is the obtained fluorescent sensing material of the embodiment of the present invention 1 and the uv absorption spectra of different metal ion in acetonitrile, and in figure, L1 represents that embodiment 1 obtains fluorescent sensing material.
As shown in Figure 10, the uv-absorbing of fluorescent sensing material when existing without metal ion that embodiment 1 is obtained does not have considerable change.
Carry out fluorescent emission intensity detection to above-mentioned obtained a series of detection sample and reference sample, fluorescent emission excitation wavelength is 360nm, shown in detected result Figure 11 and Figure 12.Figure 11 is the obtained fluorescent sensing material of the embodiment of the present invention 1 and the fluorescent emission spectrogram of different metal ion in acetonitrile, and in figure, L1 represents that embodiment 1 obtains fluorescent sensing material; Figure 12 is that the embodiment of the present invention 1 obtains fluorescent sensing material and the Fluorescence Increasing multiple figure of different metal ion in acetonitrile, and in figure, F represents fluorescence intensity, F
0represent the fluorescence intensity of reference sample.
From Figure 11 and Figure 12, at Pd
2+when ion exists, the fluorescent emission intensity of the acetonitrile solution of the fluorescent sensing material that embodiment 1 is obtained has and significantly weakens; When other metal ions exist, the fluorescent emission intensity of the acetonitrile solution of the fluorescent sensing material that embodiment 1 is obtained slightly strengthens.Illustrate that the obtained fluorescent sensing material of embodiment 1 is to Pd
2+the identification of ion has good selectivity.
Embodiment 14
Different palladium class material is on the impact experiment of the fluorescent sensing material fluorescent emission intensity that embodiment 1 obtains
With 10
-4fluorescent sensing material prepared by mmol embodiment 1 and the solution that is mixed to get of 10mL acetonitrile as reference sample, with 5 × 10
-4mmol PdCl
2, 10
-4fluorescent sensing material prepared by mmol embodiment 1 and the solution that 10mL acetonitrile is mixed to get detect sample, with 5 × 10 as first
-4mmol Pd (dba)
2, 10
-4fluorescent sensing material prepared by mmol embodiment 1 and the solution that 10mL acetonitrile is mixed to get detect sample, with 5 × 10 as second
-4mmol PdCl
2(dppf), 10
-4fluorescent sensing material prepared by mmol embodiment 1 and the solution that 10mL acetonitrile is mixed to get detect sample, with 5 × 10 as the 3rd
-4mmol Pd (OAc)
2, 10
-4fluorescent sensing material prepared by mmol embodiment 1 and the solution that 10mL acetonitrile is mixed to get detect sample as the 4th.
Use fluorescence emission spectrometer to detect the fluorescent emission intensity that reference sample, first detects sample, the second detection sample, the 3rd detects sample and the 4th detection sample respectively, result as shown in figure 13.Figure 13 fluorescent emission intensity histogram that is the obtained fluorescent sensing material of the embodiment of the present invention 1 in containing the solution of different palladium material, in figure, A is reference sample, B is the first detection sample, C is the second detection sample, D be the 3rd detect sample, E the 4th detects sample.
As seen in Figure 13, the fluorescent emission intensity of B, C, D and E is starkly lower than A, illustrate that the fluorescent sensing material that embodiment 1 obtains all can occur the phenomenon that fluorescence intensity reduces under zeroth order palladium or divalent palladium exist, the fluorescence sense that embodiment 1 obtains can be used in the detection of zeroth order palladium or divalent palladium.
Embodiment 15
Different metal ion and Pd
2+the system that coexists is on the impact experiment of the fluorescent sensing material fluorescent emission intensity that embodiment 1 obtains
Prepare reference sample according to the proportioning in table 2 and detect sample.
Table 2 detects the component proportion table of sample and reference sample
Note: in table 2, L1 represents the fluorescent sensing material that embodiment 1 is obtained.
Carry out fluorescent emission intensity detection to reference sample and detection sample, fluorescent emission excitation wavelength is 360nm, and detected result as shown in figure 14.Figure 14 is the obtained fluorescent sensing material of the embodiment of the present invention 1 and the variation diagram of the fluorescent emission intensity of different metal ion in acetonitrile, and wherein, figure A is fluorescent emission intensity histogram, and figure B is Fluorescence Increasing multiple figure, and scheme in B, F represents fluorescence intensity, F
0represent the fluorescence intensity of reference sample 1.
As seen in Figure 14, the fluorescent sensing material that embodiment 1 is obtained is at different metal ion and Pd
2+fluorescence intensity under coexisting has and significantly reduces phenomenon, illustrates that the obtained fluorescent sensing material of embodiment 1 is to Pd
2+detection have good immunity from interference.
Embodiment 16
The impact experiment of the fluorescent sensing material uv-absorbing intensity that different metal ion pair embodiment 2 is obtained and fluorescent emission intensity
Respectively by 5 × 10
-4the PtCl of mmol
2, HgCl
2, ZnCl
2, SnCl
2, RuCl
3, PbCl
2, NiCl
2, NaCl, MgCl
2, LiCl, KCl, FeCl
3, CuCl
2, CoCl
2, CdCl
2, CaCl
2, BaCl
2with 10
-4the fluorescent sensing material that mmol embodiment 2 is obtained and the mixing of 10mL acetonitrile, detect its uv-absorbing intensity and fluorescent emission intensity, fluorescent emission excitation wavelength is 360nm, and result as shown in Figure 15 and Figure 16.Figure 15 is the obtained fluorescent sensing material of the embodiment of the present invention 2 and the uv absorption spectra of different metal ion in acetonitrile.Figure 16 is the obtained fluorescent sensing material of the embodiment of the present invention 2 and the fluorescent emission spectrogram of different metal ion in acetonitrile.
As shown in Figure 15, the uv-absorbing of fluorescent sensing material when existing without metal ion that embodiment 2 is obtained does not have considerable change.As shown in Figure 16, at Pd
2+when existing, the fluorescent emission intensity of the acetonitrile solution of the fluorescent sensing material that embodiment 2 is obtained has and significantly weakens; When other metal ions exist, the fluorescent emission intensity of the acetonitrile solution of the fluorescent sensing material that embodiment 2 is obtained slightly strengthens.Illustrate that the obtained fluorescent sensing material of embodiment 2 is to Pd
2+identification have good selectivity.
Embodiment 17
Different palladium class material is on the impact experiment of the fluorescent sensing material fluorescent emission intensity that embodiment 2 obtains
With 10
-4fluorescent sensing material prepared by mmol embodiment 2 and the solution that is mixed to get of 10mL acetonitrile as reference sample, with 5 × 10
-4mmol PdCl
2, 10
-4fluorescent sensing material prepared by mmol embodiment 2 and the solution that 10mL acetonitrile is mixed to get detect sample, with 5 × 10 as first
-4mmol Pd (dba)
2, 10
-4fluorescent sensing material prepared by mmol embodiment 2 and the solution that 10mL acetonitrile is mixed to get detect sample, with 5 × 10 as second
-4mmol Pd (OAc)
2, 10
-4fluorescent sensing material prepared by mmol embodiment 2 and the solution that 10mL acetonitrile is mixed to get detect sample as the 3rd.
Use fluorescence emission spectrometer to detect sample, the second detection sample and the 3rd fluorescent emission intensity detecting sample to reference sample, first respectively to detect, result as shown in figure 17.Figure 17 is obtained fluorescent sensing material fluorescent emission intensity histogram in containing the solution of different palladium material of the embodiment of the present invention 2, and in figure, 1 for reference sample, 2, be the first detection sample, 3 to be the second detection sample, 4 be the 3rd detects sample.
As seen in Figure 17,2, the fluorescent emission intensity of 3 and 4 is starkly lower than 1, illustrate that the fluorescent sensing material that embodiment 2 obtains all can occur the phenomenon that fluorescence intensity reduces under zeroth order palladium or divalent palladium exist, the fluorescence sense that embodiment 2 obtains can be used in the detection of zeroth order palladium or divalent palladium.
Embodiment 18
The impact experiment of the fluorescent sensing material uv-absorbing intensity that different metal ion pair embodiment 3 is obtained and fluorescent emission intensity
Respectively by 5 × 10
-4the PtCl of mmol
2, HgCl
2, ZnCl
2, SnCl
2, RuCl
3, PbCl
2, NiCl
2, NaCl, MgCl
2, LiCl, KCl, FeCl
3, CuCl
2, CoCl
2, CdCl
2, CaCl
2, BaCl
2with 10
-4the fluorescent sensing material that mmol embodiment 3 is obtained and the mixing of 10mL acetonitrile, detect its uv-absorbing intensity and fluorescent emission intensity, fluorescent emission excitation wavelength is 360nm, and result as shown in Figure 18 and Figure 19.Figure 18 is the obtained fluorescent sensing material of the embodiment of the present invention 3 and the uv absorption spectra of different metal ion in acetonitrile.Figure 19 is the obtained fluorescent sensing material of the embodiment of the present invention 3 and the fluorescent emission spectrogram of different metal ion in acetonitrile.
As shown in Figure 18, the uv-absorbing of fluorescent sensing material when existing without metal ion that embodiment 3 is obtained does not have considerable change.As shown in Figure 19, at Pd
2+when ion exists, the fluorescent emission intensity of the acetonitrile solution of the fluorescent sensing material that embodiment 3 is obtained has and significantly weakens; When other metal ions exist, the fluorescent emission intensity of the acetonitrile solution of the fluorescent sensing material that embodiment 3 is obtained slightly strengthens.Illustrate that the obtained fluorescent sensing material of embodiment 3 is to Pd
2+the identification of ion has good selectivity.
Embodiment 19
Different palladium class material is on the impact experiment of the fluorescent sensing material fluorescent emission intensity that embodiment 3 obtains
With 10
-4fluorescent sensing material prepared by mmol embodiment 3 and the solution that is mixed to get of 10mL acetonitrile as reference sample, with 5 × 10
-4mmol PdCl
2, 10
-4fluorescent sensing material prepared by mmol embodiment 3 and the solution that 10mL acetonitrile is mixed to get detect sample, with 5 × 10 as first
-4mmol Pd (dba)
2, 10
-4fluorescent sensing material prepared by mmol embodiment 3 and the solution that 10mL acetonitrile is mixed to get detect sample, with 5 × 10 as second
-4mmol Pd (OAc)
2, 10
-4fluorescent sensing material prepared by mmol embodiment 3 and the solution that 10mL acetonitrile is mixed to get detect sample as the 3rd.
Use fluorescence emission spectrometer to detect sample, the second detection sample and the 3rd fluorescent emission intensity detecting sample to reference sample, first respectively to detect, result as shown in figure 20.Figure 20 is obtained fluorescent sensing material fluorescent emission intensity histogram in containing the solution of different palladium material of the embodiment of the present invention 3, and in figure, 1 for reference sample, 2, be the first detection sample, 3 to be the second detection sample, 4 be the 3rd detects sample.
As seen in Figure 20,2, the fluorescent emission intensity of 3 and 4 is starkly lower than 1, illustrate that the fluorescent sensing material that embodiment 3 obtains all can occur the phenomenon that fluorescence intensity reduces under zeroth order palladium or divalent palladium exist, the fluorescence sense that embodiment 3 obtains can be used in the detection of zeroth order palladium or divalent palladium.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a fluorescent sensing material, has formula (I) structure:
Wherein, R
1, R
2and R
3independently selected from hydrogen, alkyl or alkoxyl group.
2. fluorescent sensing material according to claim 1, is characterized in that, described R
1, R
2and R
3independently selected from hydrogen, C
1~ C
10alkyl or C
1~ C
10alkoxyl group.
3. fluorescent sensing material according to claim 1, is characterized in that, described R
1, R
2and R
3identical.
4. a preparation method for fluorescent sensing material, comprises the following steps:
A), mono-cyclic aromatic aldehyde, 2-cyanopyridine and ammonium salt mix in a solvent, and the mixture be mixed to get heats, and obtains the fluorescent sensing material of structure shown in formula (I);
Wherein, R
1, R
2and R
3independently selected from hydrogen, alkyl or alkoxyl group;
Described mono-cyclic aromatic aldehyde is phenyl aldehyde, to one or more in alkylbenzaldehyde and p-alkoxybenzaldehydes.
5. preparation method according to claim 4, is characterized in that, described mono-cyclic aromatic aldehyde is phenyl aldehyde, to alkylbenzaldehyde or p-alkoxybenzaldehydes.
6. preparation method according to claim 4, is characterized in that, described ammonium salt is one or more in ammonium acetate, ammonium chloride, ammonium nitrate, ammonium sulfate and volatile salt.
7. preparation method according to claim 4, is characterized in that, the mol ratio of described 2-cyanopyridine, mono-cyclic aromatic aldehyde and ammonium salt is 1:1 ~ 4:2 ~ 6.
8. according to the preparation method shown in claim 4, it is characterized in that, the temperature of described heating is 70 ~ 120 DEG C.
9. according to the preparation method shown in claim 4, it is characterized in that, the mode of described heating is microwave exposure.
10. a detection method for palladium class material, comprises the following steps:
By fluorescent sensing material, testing sample and solvent described in any one of claims 1 to 3, detect the fluorescence intensity of gained mixture;
By described fluorescent sensing material and described solvent, detect the fluorescence intensity of gained solution;
If the fluorescence intensity of gained mixture is lower than the fluorescence intensity of gained solution, then contain zeroth order palladium and/or divalent palladium in described testing sample, otherwise not containing zeroth order palladium and/or divalent palladium in described testing sample.
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