CN104371709B - A kind of fluorescent sensing material and its preparation method and application - Google Patents
A kind of fluorescent sensing material and its preparation method and application Download PDFInfo
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- CN104371709B CN104371709B CN201410657264.4A CN201410657264A CN104371709B CN 104371709 B CN104371709 B CN 104371709B CN 201410657264 A CN201410657264 A CN 201410657264A CN 104371709 B CN104371709 B CN 104371709B
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Abstract
The application belongs to chemical sensing material field, particularly relates to a kind of fluorescent sensing material and its preparation method and application.The fluorescent sensing material that the present invention provides, has formula (I) structure, wherein, R1、R2And R3Independently selected from hydrogen, alkyl or alkoxyl.The fluorescent sensing material that the present invention provides can well form complex with zeroth order palladium, divalent palladium in the solution, so that this fluorescent sensing material fluorescent quenching, reaches to detect zeroth order palladium and the purpose of divalent palladium.It addition, this fluorescent sensing material is being formed during complex will not had the highest selectivity to palladium by other the metal ion disturbance such as mercury ion, platinum ion with palladium.Test result indicate that, the fluorescent sensing material that the present invention provides has the highest selectivity and anti-interference to the detection of zeroth order palladium and divalent palladium.
Description
Technical field
The invention belongs to chemical sensing material field, particularly relate to a kind of fluorescent sensing material and preparation side thereof
Method and application.
Background technology
Along with industry, agricultural and the development of urbanization process, heavy metal (HMs) agricultural,
The application in chemical industrie field is also constantly expanding.As the one in heavy metal, palladium electronics industry,
Auto industry, jewellery industry and chemical catalysis field all play important role, but palladium in product simultaneously
Residue problem the most day by day annoying people, threaten human health.Research shows, palladium class material with contain
The amino acid of sulphur, protein, DNA and other biomolecule have preferable complexing power, it has also become
Being only second to the second largest metal carcinogenic substance of nickel, particularly palladium bichloride, eyes and skin to people suffer from very
Strong excitant.Therefore, palladium class material, the especially detection of zeroth order palladium and divalent palladium are become grind
The focus that the person of studying carefully study.
The method of traditional detection palladium has atomic absorption spectrography (AAS) (AAS), inductively coupled plasma former
Sub-emission spectrometry (ICP-AES), SPME-high performance liquid chromatography (SPME-HPLC) and
X-ray fluorescence method (XRF) etc..Although these methods can quickly analyze the existence of palladium class material
And have high sensitivity, but they typically require the sample pretreatment process of complexity, strict experiment
Condition, costly and complicated instrument and veteran operating personnel.Therefore, have cheap,
Simple to operate, high sensitivity and selective fluorescence sense technology are increasingly paid attention to by people.This technology
Ion can be detected delicately by launching light color and Strength Changes.To having excellent detection performance
The exploitation of fluorescent sensing material receives much concern.
Although the fluorescent sensing material for palladium detection of more existing function admirables is developed, but existing
The fluorescent sensing material detection for palladium detection having is only capable of individually for zeroth order palladium or the inspection of divalent palladium
Survey, zeroth order palladium and divalent palladium can not be detected simultaneously.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of fluorescent sensing material and preparation method thereof and answer
With, the fluorescent sensing material that the present invention provides can detect zeroth order palladium and divalent palladium simultaneously.
The invention provides a kind of fluorescent sensing material, there is formula (I) structure:
Wherein, R1、R2And R3Independently selected from hydrogen, alkyl or alkoxyl.
Preferably, described R1、R2And R3Independently selected from hydrogen, C1～C10Alkyl or C1～C10Alkane
Epoxide.
Preferably, described R1、R2And R3Identical.
The invention provides the preparation method of a kind of fluorescent sensing material, comprise the following steps:
A), mono-cyclic aromatic aldehyde, 2-cyanopyridine and ammonium salt mix in a solvent, the mixture being mixed to get
Heat, obtain the fluorescent sensing material of structure shown in formula (I)；
Wherein, R1、R2And R3Independently selected from hydrogen, alkyl or alkoxyl；
Described mono-cyclic aromatic aldehyde is benzaldehyde, to the one in alkylbenzaldehyde and p-alkoxybenzaldehydes or
Multiple.
Preferably, described mono-cyclic aromatic aldehyde be benzaldehyde, to alkylbenzaldehyde or p-alkoxybenzaldehydes.
Preferably, during described ammonium salt is ammonium acetate, ammonium chloride, ammonium nitrate, ammonium sulfate and ammonium carbonate
Plant or multiple.
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 irradiation.
The invention provides the detection method of a kind of palladium class material, comprise the following steps:
Fluorescent sensing material mentioned above, testing sample and solvent are mixed, detection gained mixture
Fluorescence intensity；
Described fluorescent sensing material and described solvent are mixed, the fluorescence intensity of detection gained solution；
If the fluorescence intensity of gained mixture is less than the fluorescence intensity of gained solution, in the most described testing sample
Containing zeroth order palladium and/or divalent palladium, without zeroth order palladium and/or divalent palladium in the most described testing sample.
Compared with prior art, the invention provides a kind of fluorescent sensing material and its preparation method and application.
The fluorescent sensing material that the present invention provides, has formula (I) structure, wherein, R1、R2And R3Select independently
From hydrogen, alkyl or alkoxyl.The fluorescent sensing material that the present invention provides in the solution can well be with zero
Valency palladium, divalent palladium form complex, so that this fluorescent sensing material fluorescent quenching, reach inspection
Survey zeroth order palladium and the purpose of divalent palladium.It addition, this fluorescent sensing material is forming complex mistake with palladium
Journey will not there be is the highest selectivity by other the metal ion disturbance such as mercury ion, platinum ion to palladium.
Test result indicate that, the detection of zeroth order palladium and divalent palladium is had very by the fluorescent sensing material that the present invention provides
High selectivity and anti-interference.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to reality
Execute the required accompanying drawing used in example or description of the prior art to be briefly described, it should be apparent that below,
Accompanying drawing in description is only embodiments of the invention, for those of ordinary skill in the art, not
On the premise of paying creative work, it is also possible to obtain other accompanying drawing 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 prepares；
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the fluorescent sensing material that the embodiment of the present invention 2 prepares；
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of the fluorescent sensing material that the embodiment of the present invention 3 prepares；
Fig. 4 is the embodiment of the present invention 1 prepared fluorescent sensing material fluorescent emission intensity in different solutions
Block diagram；
Fig. 5 is the embodiment of the present invention 2 prepared fluorescent sensing material fluorescent emission intensity in different solutions
Block diagram；
Fig. 6 is the embodiment of the present invention 3 prepared fluorescent sensing material fluorescent emission intensity in different solutions
Block diagram；
Fig. 7 is the fluorescent sensing material for preparing of the embodiment of the present invention 1 UV absorption in different solvents and glimmering
Light emission spectrum figure；
Fig. 8 is that the prepared fluorescent sensing material of the embodiment of the present invention 1 is at different Pd2+In the acetonitrile solution of concentration
Fluorescent emission spectrogram；
Fig. 9 is the embodiment of the present invention 1 prepared fluorescent sensing material and Pd2+Job ' s plot curve；
Figure 10 be the fluorescent sensing material for preparing of the embodiment of the present invention 1 with different metal ion in acetonitrile
Uv absorption spectra；
Figure 11 be the fluorescent sensing material for preparing of the embodiment of the present invention 1 with different metal ion in acetonitrile
Fluorescent emission spectrogram；
Figure 12 be the fluorescent sensing material for preparing of the embodiment of the present invention 1 with different metal ion in acetonitrile
Fluorescence Increasing multiple figure；
Figure 13 is that the fluorescent sensing material that the embodiment of the present invention 1 prepares is glimmering in the solution containing different palladium materials
Light emissive porwer block diagram；
Figure 14 be the fluorescent sensing material for preparing of the embodiment of the present invention 1 with different metal ion in acetonitrile
The variation diagram of fluorescent emission intensity；
Figure 15 be the fluorescent sensing material for preparing of the embodiment of the present invention 2 with different metal ion in acetonitrile
Uv absorption spectra；
Figure 16 be the fluorescent sensing material for preparing of the embodiment of the present invention 2 with different metal ion in acetonitrile
Fluorescent emission spectrogram；
Figure 17 is that the fluorescent sensing material that the embodiment of the present invention 2 prepares is glimmering in the solution containing different palladium materials
Light emissive porwer block diagram；
Figure 18 be the fluorescent sensing material for preparing of the embodiment of the present invention 3 with different metal ion in acetonitrile
Uv absorption spectra；
Figure 19 be the fluorescent sensing material for preparing of the embodiment of the present invention 3 with different metal ion in acetonitrile
Fluorescent emission spectrogram；
Figure 20 is that the fluorescent sensing material that the embodiment of the present invention 3 prepares is glimmering in the solution containing different palladium materials
Light emissive porwer block diagram.
Detailed description of the invention
Technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that institute
The embodiment described is only a part of embodiment of the present invention rather than whole embodiments.Based on this
Embodiment in bright, those of ordinary skill in the art are obtained under not making creative work premise
Every other embodiment, broadly falls into the scope of protection of the invention.
The invention provides a kind of fluorescent sensing material, there is formula (I) structure:
Wherein, R1、R2And R3Independent selected from hydrogen, alkyl or alkoxyl.
The fluorescent sensing material that the present invention provides has formula (I) structure.Wherein, R1、R2And R3Independently
Selected from hydrogen, alkyl or alkoxyl, it preferably is selected from hydrogen, C1～C10Alkyl or C1～C10Alkoxyl, more preferably
From hydrogen, C1～C5Alkyl or C1～C5Alkoxyl, most preferably from hydrogen, methyl or methoxy.At this
In some bright embodiment, described R1、R2And R3The most identical.
In the present invention, described fluorescent sensing material is specifically as follows formula (II), formula (III) and formula (IV)
One in shown structural compounds:
The fluorescent sensing material that the present invention provides can well be formed with zeroth order palladium, divalent palladium in the solution
Complex, so that this fluorescent sensing material fluorescent quenching, reaches to detect zeroth order palladium and divalent palladium
Purpose.It addition, this fluorescent sensing material with palladium formed during complex will not by mercury from
Other the metal ion disturbance such as son, platinum ion, has the highest selectivity to palladium.
The invention provides the preparation method of a kind of fluorescent sensing material, comprise the following steps:
A), mono-cyclic aromatic aldehyde, 2-cyanopyridine and ammonium salt mix in a solvent, the mixture being mixed to get
Heat, obtain the fluorescent sensing material of structure shown in formula (I)；
Wherein, R1、R2And R3Independently selected from hydrogen, alkyl or alkoxyl；
Described mono-cyclic aromatic aldehyde is benzaldehyde, to the one in alkylbenzaldehyde and p-alkoxybenzaldehydes or
Multiple.
In the preparation method of the offer of the present invention, first mono-cyclic aromatic aldehyde, 2-cyanopyridine and ammonium salt are existed
Solvent mixes.Wherein, described mono-cyclic aromatic aldehyde be benzaldehyde, to alkylbenzaldehyde and palkoxy benzene
One or more in formaldehyde, preferably benzaldehyde, to alkylbenzaldehyde or p-alkoxybenzaldehydes.Institute
State alkylbenzaldehyde is preferably p-tolyl aldehyde, p-ethylbenzaldehyde, to propylbenzaldehyde, to fourth
Benzaldehyde, to amylbenzene formaldehyde, to hexylbenzaldehyde, to heptyl benzene formaldehyde, to octyl group benzaldehyde,
To nonyl benzene formaldehyde or to decyl benzaldehyde.Described p-alkoxybenzaldehydes be preferably P-methoxybenzal-dehyde,
P-ethoxybenzaldehyde, to propoxybenzaldehyde, to butoxybenzaldehyde, to pentyloxybenzaldehyde, right
Hexyloxybenzaldehyde, to heptyloxybenzaldehyde, to octyloxybenzaldehyde, to nonyl epoxide benzaldehyde or to the last of the ten Heavenly stems
Epoxide benzaldehyde.Described solvent is preferably dimethyl fumarate.Described ammonium salt is preferably ammonium acetate, chlorination
One or more in ammonium, ammonium nitrate, ammonium sulfate and ammonium carbonate.Described 2-cyanopyridine, mono-cyclic aromatic aldehyde
It is preferably 1:1～4:2～6, more preferably 1:2.5:4 with the mol ratio of ammonium salt.
After mono-cyclic aromatic aldehyde, 2-cyanopyridine and ammonium salt mix in a solvent, mixed to be mixed to get
Compound heats.The temperature of described heating is preferably 70～120 DEG C.The mode of described heating can be oil
Bath, it is also possible to for microwave irradiation, preferably microwave irradiation.In the present invention, it is oil bath when mode of heating
Time, the time of heating is preferably 7～8h；When mode of heating is microwave irradiation, 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
Adding water, cancellation is reacted, and obtains reaction product solution.Described reaction product solution post-processes,
To the fluorescent sensing material of structure shown in formula (I).The concrete mode of described post processing be preferably: described instead
Answer reaction mixture to sequentially pass through extraction, wash, be dried, revolve steaming, column chromatography and recrystallization, obtain formula (I)
The fluorescent sensing material of shown structure.The extractant of described extraction is preferably ethyl acetate；Described washing
Washing agent is preferably saturated aqueous common salt；Described dry drier is preferably anhydrous sodium sulfate；Described heavy knot
Brilliant solvent is preferably acetonitrile.
The present invention, with raw material cheap and easy to get, is preparing fluorescent sensing material without next step method of catalysts conditions,
Step is simple, and processing ease, prepared fluorescent sensing material is that a class can detect zeroth order palladium and two simultaneously
The fluorescent sensing material of the high sensitivity of valency palladium.
The invention provides the detection method of a kind of palladium class material, comprise the following steps:
Fluorescent sensing material mentioned above, testing sample and solvent are mixed, detects the glimmering of gained solution
Luminous intensity；
Described fluorescent sensing material and described solvent are mixed, the fluorescence intensity of detection gained solution；
If the fluorescence intensity of gained mixture is less than the fluorescence intensity of gained solution, in the most described testing sample
Containing zeroth order palladium and/or divalent palladium, without zeroth order palladium and/or divalent palladium in the most described testing sample.
The present invention provide detection method in, by fluorescent sensing material mentioned above, testing sample and
Solvent mixes, after mixing, and the fluorescence intensity of detection gained mixture.Described solvent is preferably acetonitrile.
The amount ratio of described fluorescent sensing material and solvent is preferably 1 (mol): 103～105(L), more preferably
It is 1 (mol): 104～105(L)。
In the present invention, the mode of described fluorescent sensing material, testing sample and solvent mixing is preferably:
Testing sample is mixed with partial solvent, obtains testing sample solution, fluorescent sensing material is molten with part
Agent mixes, and obtains fluorescent sensing material solution, then by the solution of described testing sample, fluorescence sense material
The solution of material and the solvent mixing of surplus.
In the embodiment that the present invention provides, described testing sample is palladium compounds, described palladium class
Compound is PdCl2、Pd(dba)2、PdCl2And Pd (OAc) (dppf)2In one or more.Described to be measured
In sample solution, the molar content of palladium compounds is 10-3～10-4mol/L.Described fluorescent sensing material solution
The molar content of middle fluorescent sensing material is 10-3～10-4mol/L.The solution of described testing sample, fluorescence pass
Palladium compounds and fluorescent sensing material in the mixture of the solution of sense material and the solvent mixing gained of surplus
Mol ratio be 0.1～5:1.
In another embodiment that the present invention provides, described testing sample is by palladium compounds and other gold
Belonging to compound composition, described palladium compounds is PdCl2、Pd(dba)2、PdCl2And Pd (OAc) (dppf)2In
One or more, other metallic compounds described are 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
One or more in salt, described platinum salt is PtCl2, described mercury salt is HgCl2, described zinc salt is ZnCl2,
Described pink salt is SnCl2, described rubidium salt is RuCl3, described lead salt is PbCl2, described nickel salt is NiCl2,
Described sodium salt is NaCl, and described magnesium salts is MgCl2, described lithium salts is LiCl, and described lithium salts is KCl, institute
Stating molysite is FeCl3, described mantoquita is CuCl2, described cobalt salt is CoCl2, described cadmium salt is CdCl2, institute
Stating calcium salt is CaCl2, described barium salt is BaCl2.Palladium compounds and other metallization in described testing sample
The mol ratio of compound 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.The solvent of the solution of described testing sample, the solution of fluorescent sensing material and surplus mixes
Closing the mol ratio content of palladium compounds and fluorescent sensing material in the mixture of gained is 0.1～5:1.
Described fluorescent sensing material and described solvent are mixed, after mixing, detects the glimmering of gained solution
Luminous intensity.The amount ratio of described fluorescent sensing material and described solvent and described fluorescent sensing material, to be measured
Sample when mixing with solvent described fluorescent sensing material identical with the amount ratio of solvent.The present invention is glimmering to detection
The equipment of luminous intensity is not particularly limited, preferably XRF.
Obtain the fluorescence intensity of described fluorescent sensing material, testing sample and solvent mixing gained mixture with
And after the fluorescence intensity of described fluorescent sensing material and solvent mixing gained solution, the fluorescence intensity to both
Value compares, if the fluorescence intensity of gained mixture is less than the fluorescence intensity of gained solution, then described in treat
Containing zeroth order palladium and/or divalent palladium in test sample product, without zeroth order palladium and/or divalence in the most described testing sample
Palladium.
The detection method that the present invention provides may be used for the detection of zeroth order palladium and divalent palladium.Test result indicate that,
The detection method that the present invention provides is high to the detection accuracy of zeroth order palladium and divalent palladium.
For the sake of becoming apparent from, it is described in detail below by following example.
Embodiment 1
By 0.265g benzaldehyde, 0.105g 2-cyanopyrimidine, 0.308g ammonium acetate and 2mL dimethyl methyl
Acid amides adds in 20mL microwave reaction pipe, reacts 30 minutes under the conditions of 100 DEG C of microwaves.Microwave spoke
After penetrating stopping, solution becomes dark, adds 5mL water, obtain reaction product solution in microwave reaction pipe.
Reaction product solution is extracted with ethyl acetate (10mL × 3), the organic phase being obtained by extraction warp successively
Supersaturation brine It, anhydrous sodium sulfate are dried and revolve steaming, obtain crude product.Crude product is again through post
Chromatography and recrystallized from acetonitrile, obtain fluorescent sensing material.
The fluorescent sensing material preparing the present embodiment carries out hydrogen nuclear magnetic resonance analysis of spectrum, result such as Fig. 1 institute
Show.Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the fluorescent sensing material that the embodiment of the present invention 1 prepares.As shown in Figure 1
Hydrogen analysis of spectrum result is:1H NMR(400MHz,DMSO)δ8.33-8.31(m,2H),7.65-7.62(m,
3H),7.41-7.38(m,4H),7.36-7.30(m,7H)。
The fluorescent sensing material preparing the present embodiment carries out carbon-13 nmr spectra analysis, and result is:13C
NMR(101MHz,DMSO)δ156.88,140.12,132.03,130.38,129.68,129.46,
128.46,128.32,127.64。
From proton nmr spectra and carbon analysis of spectrum result, the fluorescent sensing material tool that the present embodiment prepares
Having formula (I) structure, R is hydrogen.
The fluorescent sensing material preparing the present embodiment carries out purity analysis and calculation of yield, and result is: produce
Rate 51%, purity 98%.
Embodiment 2
By 0.300g p-tolyl aldehyde, 0.105g 2-cyanopyrimidine, 0.308g ammonium acetate and 2mL bis-
NMF adds in 20mL microwave reaction pipe, reacts 30 minutes under the conditions of 100 DEG C of microwaves.
After microwave stops, solution becomes dark, adds 5mL water in microwave reaction pipe, obtains reaction and produces
Thing solution.
Reaction product solution is extracted with ethyl acetate (10mL × 3), the organic phase being obtained by extraction warp successively
Supersaturation brine It, anhydrous sodium sulfate are dried and revolve steaming, obtain crude product.Crude product is again through post
Chromatography and recrystallized from acetonitrile, obtain fluorescent sensing material.
The fluorescent sensing material preparing the present embodiment carries out hydrogen nuclear magnetic resonance analysis of spectrum, result such as Fig. 2 institute
Show.Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the fluorescent sensing material that the embodiment of the present invention 2 prepares.As shown in Figure 2
Hydrogen analysis of spectrum result is: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 preparing the present embodiment carries out carbon-13 nmr spectra analysis, and result is:13C
NMR(101MHz,DMSO)δ157.03,149.11,146.50,141.44,140.51,138.18,137.77,
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 analysis of spectrum result, the fluorescent sensing material tool that the present embodiment prepares
Having formula (I) structure, R is methyl.
The fluorescent sensing material preparing the present embodiment carries out purity analysis and calculation of yield, and result is: produce
Rate 30%, purity 98%.
Embodiment 3
By 0.340g P-methoxybenzal-dehyde, 0.105g 2-cyanopyrimidine, 0.308g ammonium acetate and 2mL bis-
NMF adds in 20mL microwave reaction pipe, reacts 30 minutes under the conditions of 100 DEG C of microwaves.
After microwave stops, solution becomes dark, adds 5mL water in microwave reaction pipe, obtains reaction and produces
Thing solution.
Reaction product solution is extracted with ethyl acetate (10mL × 3), the organic phase being obtained by extraction warp successively
Supersaturation brine It, anhydrous sodium sulfate are dried and revolve steaming, obtain crude product.Crude product is again through post
Chromatography and recrystallized from acetonitrile, obtain fluorescent sensing material.
The fluorescent sensing material preparing the present embodiment carries out hydrogen nuclear magnetic resonance analysis of spectrum, result such as Fig. 3 institute
Show.Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of the fluorescent sensing material that the embodiment of the present invention 3 prepares.As shown in Figure 3
Hydrogen analysis of spectrum result is:1H NMR(400MHz,CDCl3) 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 preparing the present embodiment carries out carbon-13 nmr spectra analysis, and result is:13C
NMR(101MHz,CDCl3)δ161.86,159.63,159.61,159.44,159.39,157.00,131.54,
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 analysis of spectrum result, the fluorescent sensing material tool that the present embodiment prepares
Having formula (I) structure, R is methoxyl group.
The fluorescent sensing material preparing the present embodiment carries out purity analysis and calculation of yield, and result is: produce
Rate 27%, purity 98%.
Embodiment 4
By 0.265g benzaldehyde, 0.105g 2-cyanopyrimidine, 0.308g ammonium acetate and 2mL dimethyl methyl
Acid amides adds in 20mL microwave reaction pipe, reacts 60 minutes under the conditions of 70 DEG C of microwaves.Microwave spoke
After penetrating stopping, solution becomes dark, adds 5mL water, obtain reaction product solution in microwave reaction pipe.
Reaction product solution is extracted with ethyl acetate (10mL × 3), the organic phase being obtained by extraction warp successively
Supersaturation brine It, anhydrous sodium sulfate are dried and revolve steaming, obtain crude product.Crude product is again through post
Chromatography and recrystallized from acetonitrile, obtain fluorescent sensing material.
The fluorescent sensing material preparing the present embodiment carries out hydrogen nuclear magnetic resonance analysis of spectrum, and result is:1H
NMR(400MHz,DMSO)δ8.33-8.31(m,2H),7.65-7.62(m,3H),7.41-7.38(m,
4H),7.36-7.30(m,7H).The fluorescent sensing material preparing the present embodiment carries out carbon-13 nmr spectra and divides
Analysis, result is:13C NMR(101MHz,DMSO)δ156.88,140.12,132.03,130.38,
129.68,129.46,128.46,128.32,127.64.From proton nmr spectra and carbon analysis of spectrum result,
The fluorescent sensing material that the present embodiment prepares has formula (I) structure, and R is hydrogen.
The fluorescent sensing material preparing the present embodiment carries out purity analysis and calculation of yield, and result is: produce
Rate 43%, purity 98%.
Embodiment 5
By 0.300g p-tolyl aldehyde, 0.105g 2-cyanopyrimidine, 0.308g ammonium acetate and 2mL bis-
NMF adds in 20mL microwave reaction pipe, reacts 10 minutes under the conditions of 120 DEG C of microwaves.
After microwave stops, solution becomes dark, adds 5mL water in microwave reaction pipe, obtains reaction and produces
Thing solution.
Reaction product solution is extracted with ethyl acetate (10mL × 3), the organic phase being obtained by extraction warp successively
Supersaturation brine It, anhydrous sodium sulfate are dried and revolve steaming, obtain crude product.Crude product is again through post
Chromatography and recrystallized from acetonitrile, obtain fluorescent sensing material.
The fluorescent sensing material preparing the present embodiment carries out hydrogen nuclear magnetic resonance analysis of spectrum, and result is:1H
NMR (400MHz, DMSO) δ 13.91 (s, 1H), 8.20 (d, J=8.1Hz, 2H), 7.43 (d, J=8.1
Hz, 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 preparing the present embodiment carries out carbon-13 nmr spectra analysis, and result is:13C
NMR(101MHz,DMSO)δ157.03,149.11,146.50,141.44,140.51,138.18,137.77,
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 analysis of spectrum result, the fluorescence that the present embodiment prepares passes
Sense material has formula (I) structure, and R is methyl.
The fluorescent sensing material preparing the present embodiment carries out purity analysis and calculation of yield, and result is: produce
Rate 29%, purity 98%.
Embodiment 6
By 0.340g P-methoxybenzal-dehyde, 0.105g 2-cyanopyrimidine, 0.308g ammonium acetate and 2mL bis-
NMF adds in 20mL reaction tube, reacts 7h in 100 DEG C of oil baths.After oil bath stops, solution
Become dark, in microwave reaction pipe, add 5mL water, obtain reaction product solution.
Reaction product solution is extracted with ethyl acetate (10mL × 3), the organic phase being obtained by extraction warp successively
Supersaturation brine It, anhydrous sodium sulfate are dried and revolve steaming, obtain crude product.Crude product is again through post
Chromatography and recrystallized from acetonitrile, obtain fluorescent sensing material.
The fluorescent sensing material preparing the present embodiment carries out hydrogen nuclear magnetic resonance analysis of spectrum, and result is:1H
NMR(400MHz,CDCl3) δ 12.79 (s, 1H), 7.78 (d, J=8.8Hz, 2H), 7.42 (d, J=6.6
Hz, 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 fluorescence sense that the present embodiment is prepared
Material carries out carbon-13 nmr spectra analysis, and result is:13C NMR(101MHz,CDCl3)δ161.86,
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.By nuclear magnetic resonance
Hydrogen spectrum and carbon analysis of spectrum result understand, and the fluorescent sensing material that the present embodiment prepares has formula (I) structure,
R is methoxyl group.
The fluorescent sensing material preparing the present embodiment carries out purity analysis and calculation of yield, and result is: produce
Rate 22%, purity 98%.
Embodiment 7
Palladium class material test experience
By 10-4The prepared fluorescent sensing material of mmol embodiment 1,10mL acetonitrile and 5 × 10-4mmol
PdCl2Mixing, obtains detecting sample 1；By 10-4The prepared fluorescent sensing material of mmol embodiment 1,10mL
Acetonitrile and 5 × 10-4mmol ZnCl2Mixing, obtains detecting sample 2；By 10-4It is glimmering that mmol embodiment 1 prepares
Light sensing material and the mixing of 10mL acetonitrile, obtain with reference to sample.
Fluorescence emission spectrometer is used respectively the fluorescent emission intensity with reference to sample and detection sample to be detected,
Result is as shown in Figure 4.Fig. 4 is glimmering in different solutions of the fluorescent sensing material for preparing of the embodiment of the present invention 1
Light emissive porwer block diagram, in figure, A is for detecting sample 1, C for detecting sample 2 with reference to sample, B.
As seen in Figure 4, the fluorescent emission intensity of the B fluorescent emission intensity significantly lower than A, C is higher than
A, illustrates to detect containing zeroth order palladium or divalent palladium in sample 1, without palladium class material in detection sample 2.Testing result
It is consistent with actual conditions, illustrates that the detection method that the present embodiment provides can accurately detect in sample and whether deposit
At palladium class material.
Embodiment 8
Palladium class material test experience
By 10-4The prepared fluorescent sensing material of mmol embodiment 2,10mL acetonitrile and 5 × 10-4mmol
Pd(dba)2Mixing, obtains detecting sample 1；By 10-4The prepared fluorescent sensing material of mmol embodiment 2,10mL
Acetonitrile and 5 × 10-4mmol PbCl2Mixing, obtains detecting sample 2；By 10-4It is glimmering that mmol embodiment 2 prepares
Light sensing material and the mixing of 10mL acetonitrile, obtain with reference to sample.
Fluorescence emission spectrometer is used respectively the fluorescent emission intensity with reference to sample and detection sample to be detected,
Result is as shown in Figure 5.Fig. 5 is glimmering in different solutions of the fluorescent sensing material for preparing of the embodiment of the present invention 2
Light emissive porwer block diagram, in figure, A is for detecting sample 1, C for detecting sample 2 with reference to sample, B.
As seen in Figure 5, the fluorescent emission intensity of the B fluorescent emission intensity significantly lower than A, C is higher than
A, illustrates to detect containing zeroth order palladium or divalent palladium in sample 1, without palladium class material in detection sample 2.Testing result
It is consistent with actual conditions, illustrates that the detection method that the present embodiment provides can accurately detect in sample and whether deposit
At palladium class material.
Embodiment 9
Palladium class material test experience
By 10-4The prepared fluorescent sensing material of mmol embodiment 3,10mL acetonitrile and 5 × 10-4mmol
Pd(OAc)2Mixing, obtains detecting sample 1；By 10-4The prepared fluorescent sensing material of mmol embodiment 3,10mL
Acetonitrile and 5 × 10-4mmol BaCl2Mixing, obtains detecting sample 2；By 10-4It is glimmering that mmol embodiment 3 prepares
Light sensing material and the mixing of 10mL acetonitrile, obtain with reference to sample.
Fluorescence emission spectrometer is used respectively the fluorescent emission intensity with reference to sample and detection sample to be detected,
Result is as shown in Figure 6.Fig. 6 is glimmering in different solutions of the fluorescent sensing material for preparing of the embodiment of the present invention 3
Light emissive porwer block diagram, in figure, A is for detecting sample 1, C for detecting sample 2 with reference to sample, B.
As seen in Figure 6, the fluorescent emission intensity of the B fluorescent emission intensity significantly lower than A, C is higher than
A, illustrates to detect containing zeroth order palladium or divalent palladium in sample 1, without palladium class material in detection sample 2.Testing result
It is consistent with actual conditions, illustrates that the detection method that the present embodiment provides can accurately detect in sample and whether deposit
At palladium class material.
Embodiment 10
The impact of fluorescent sensing material UV absorption intensity and fluorescent emission intensity is tested by different solvents
Respectively by the dichloromethane of 10mL, ethanol, acetonitrile, oxolane, toluene and 10-4Mmol implements
The fluorescent sensing material mixing that example 1 prepares, detects its UV absorption intensity and fluorescent emission intensity, and fluorescence is sent out
Penetrating excitation wavelength is 360nm, and result is as shown in Figure 7.Fig. 7 is the fluorescence sense that the embodiment of the present invention 1 prepares
Material UV absorption in different solvents and fluorescent emission spectrogram.
As seen in Figure 7, the fluorescent sensing material that embodiment 1 prepares ultraviolet in different solvents is inhaled
Receive and fluorescence emission wavelengths scope does not has significant change.The fluorescent sensing material that embodiment 1 prepares is in ethanol
Fluorescent emission intensity the strongest, the fluorescent emission intensity in acetonitrile is the most weak.
Embodiment 11
Different Pd2+The impact of fluorescent sensing material fluorescent emission intensity is tested by concentration
It is 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/L2Acetonitrile solution 10mL and 10-4Mmol embodiment 1 prepares fluorescent sensing material
Mixing, detects its fluorescent emission intensity, and fluorescent emission excitation wavelength is 360nm, and result is as shown in Figure 8.
Fig. 8 is that the prepared fluorescent sensing material of the embodiment of the present invention 1 is at different Pd2+Glimmering in the acetonitrile solution of concentration
Light emission spectrum figure, in figure, 0 equivalent PdCl2Represent in detection sample without PdCl2, 5 equivalent PdCl2Represent inspection
PdCl in test sample2Concentration be 5 × 10-5mol/L。
As seen in Figure 8, along with PdCl2The increase of concentration, the fluorescent sensing material that embodiment 1 prepares
Fluorescence intensity gradually weaken.
Embodiment 12
Fluorescent sensing material and Pd2+Mensuration in conjunction with 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 prepares | PtCl2/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 |
The fluorescence sense intensity of 11 test specimens in detection table 1, and draw Job ' s according to fluorescence sense intensity level
Plot curve.Job ' s plot curve is as it is shown in figure 9, Fig. 9 is the fluorescence sense material that the embodiment of the present invention 1 prepares
Material and Pd2+Job ' s plot curve, wherein, XPd=CPd/(CPd+CL1), CPdFor Pd in test specimens2+Rub
That concentration, CL1Molar concentration for the fluorescent sensing material that embodiment in test specimens 1 prepares；I0It it is the first survey
The fluorescent emission intensity value of sample；I represents the fluorescent emission intensity value of test specimens.
As seen in Figure 9, embodiment 1 prepared fluorescent sensing material and Pd2+It is 1:1 in conjunction with ratio.
Embodiment 13
Different metal ion pair embodiment 1 prepared fluorescent sensing material UV absorption intensity and fluorescent emission
The impact experiment of intensity
Respectively by 5 × 10-4The PtCl of mmol2、HgCl2、ZnCl2、SnCl2、RuCl3、PbCl2、NiCl2、
NaCl、MgCl2、LiCl、KCl、FeCl3、CuCl2、CoCl2、CdCl2、CaCl2、BaCl2With 10-4
Fluorescent sensing material and 10mL acetonitrile that mmol embodiment 1 prepares mix, and obtain a series of detection sample；Will
10-4Fluorescent sensing material and 10mL acetonitrile that mmol embodiment 1 prepares mix, and obtain with reference to sample.
Above-mentioned prepared a series of detection samples are carried out UV absorption strength detection, testing result such as figure
Shown in 10.Figure 10 be the fluorescent sensing material for preparing of the embodiment of the present invention 1 with different metal ion in acetonitrile
Uv absorption spectra, in figure, L1 represents that embodiment 1 prepares fluorescent sensing material.
As shown in Figure 10, the fluorescent sensing material that embodiment 1 prepares is without the ultraviolet in the presence of metal ion
Absorption does not has significant change.
To above-mentioned prepared a series of detection samples and carry out fluorescent emission intensity detection, fluorescent emission with reference to sample
Excitation wavelength is shown in 360nm, testing result Figure 11 and Figure 12.Figure 11 is that the embodiment of the present invention 1 prepares
Fluorescent sensing material and different metal ion fluorescent emission spectrogram in acetonitrile, in figure, L1 represents embodiment 1
Prepare fluorescent sensing material；Figure 12 is that the embodiment of the present invention 1 prepares fluorescent sensing material and different metal ion
Fluorescence Increasing multiple figure in acetonitrile, in figure, F represents fluorescence intensity, F0Represent that the fluorescence with reference to sample is strong
Degree.
From Figure 11 and Figure 12, at Pd2+In the presence of ion, the fluorescent sensing material that embodiment 1 prepares
The fluorescent emission intensity of acetonitrile solution has and significantly weakens；In the presence of other metal ions, embodiment 1 prepares
The fluorescent emission intensity of acetonitrile solution of fluorescent sensing material slightly strengthen.Illustrate that embodiment 1 prepares glimmering
Light sensing material is to Pd2+The identification of ion has good selectivity.
Embodiment 14
The impact experiment on the fluorescent sensing material fluorescent emission intensity that embodiment 1 prepares of the different palladium class materials
With 10-4The solution that the fluorescent sensing material of mmol embodiment 1 preparation and 10mL acetonitrile are mixed to get is made
For with reference to sample, with 5 × 10-4mmol PdCl2、10-4The fluorescent sensing material and 10 of mmol embodiment 1 preparation
The solution that mL acetonitrile is mixed to get is as the first detection sample, with 5 × 10-4mmol Pd(dba)2、10-4mmol
The solution that the fluorescent sensing material of embodiment 1 preparation and 10mL acetonitrile are mixed to get detects sample as second, with
5×10-4mmol PdCl2(dppf)、10-4The fluorescent sensing material of mmol embodiment 1 preparation and 10mL acetonitrile
The solution being mixed to get is as the 3rd detection sample, with 5 × 10-4mmol Pd(OAc)2、10-4Mmol embodiment
The solution that the fluorescent sensing material of 1 preparation and 10mL acetonitrile are mixed to get is as the 4th detection sample.
Use fluorescence emission spectrometer respectively to reference to sample, the first detection sample, the second detection sample, the 3rd inspection
The fluorescent emission intensity of test sample and the 4th detection sample detects, and result is as shown in figure 13.Figure 13 is this
The fluorescent sensing material that bright embodiment 1 prepares fluorescent emission intensity column in the solution containing different palladium materials
Figure, in figure A for reference to sample, B be the first detection sample, C be the second detection sample, D be the 3rd to detect sample, E
It it is the 4th detection sample.
As seen in Figure 13, the fluorescent emission intensity of B, C, D and E is significantly lower than A, illustrates to implement
The fluorescent sensing material that example 1 prepares all can occur that in the presence of zeroth order palladium or divalent palladium fluorescence intensity reduces
Phenomenon, the fluorescence sense that embodiment 1 prepares can be used in the detection of zeroth order palladium or divalent palladium.
Embodiment 15
Different metal ion and Pd2+The fluorescent sensing material fluorescent emission that embodiment 1 is prepared by the system that coexists is strong
The impact experiment of degree
Prepare with reference to sample and detection sample according to the proportioning in table 2.
Table 2 detects sample and the component proportion table with reference to sample
Note: in table 2, L1 represents the fluorescent sensing material that embodiment 1 prepares.
Carrying out fluorescent emission intensity detection to reference to sample and detection sample, fluorescent emission excitation wavelength is 360nm,
Testing result is as shown in figure 14.Figure 14 is the embodiment of the present invention 1 prepared fluorescent sensing material and different metal
The variation diagram of ion fluorescent emission intensity in acetonitrile, wherein, figure A is fluorescent emission intensity block diagram,
Figure B is Fluorescence Increasing multiple figure, and in figure B, F represents fluorescence intensity, F0Represent the fluorescence intensity with reference to sample 1.
As seen in Figure 14, the fluorescent sensing material that embodiment 1 prepares is at different metal ion and Pd2+
Fluorescence intensity under coexisting has and significantly reduces phenomenon, and the fluorescent sensing material pair that embodiment 1 prepares is described
Pd2+Detection have good antijamming capability.
Embodiment 16
Different metal ion pair embodiment 2 prepared fluorescent sensing material UV absorption intensity and fluorescent emission
The impact experiment of intensity
Respectively by 5 × 10-4The PtCl of mmol2、HgCl2、ZnCl2、SnCl2、RuCl3、PbCl2、NiCl2、
NaCl、MgCl2、LiCl、KCl、FeCl3、CuCl2、CoCl2、CdCl2、CaCl2、BaCl2With 10-4
Fluorescent sensing material that mmol embodiment 2 prepares and the mixing of 10mL acetonitrile, detect its UV absorption intensity and
Fluorescent emission intensity, fluorescent emission excitation wavelength is 360nm, and result is as shown in Figure 15 and Figure 16.Figure 15
It is the prepared fluorescent sensing material of the embodiment of the present invention 2 and different metal ion UV absorption in acetonitrile
Spectrogram.Figure 16 be the fluorescent sensing material for preparing of the embodiment of the present invention 2 with different metal ion in acetonitrile
Fluorescent emission spectrogram.
As shown in Figure 15, the fluorescent sensing material that embodiment 2 prepares is without the ultraviolet in the presence of metal ion
Absorption does not has significant change.As shown in Figure 16, at Pd2+In the presence of, the fluorescence sense material that embodiment 2 prepares
The fluorescent emission intensity of acetonitrile solution of material has and significantly weakens；In the presence of other metal ions, embodiment 2
The fluorescent emission intensity of the acetonitrile solution of the fluorescent sensing material prepared slightly strengthens.Illustrate that embodiment 2 prepares
Fluorescent sensing material to Pd2+Identification have good selectivity.
Embodiment 17
The impact experiment on the fluorescent sensing material fluorescent emission intensity that embodiment 2 prepares of the different palladium class materials
With 10-4The solution that the fluorescent sensing material of mmol embodiment 2 preparation and 10mL acetonitrile are mixed to get is made
For with reference to sample, with 5 × 10-4mmol PdCl2、10-4The fluorescent sensing material and 10 of mmol embodiment 2 preparation
The solution that mL acetonitrile is mixed to get is as the first detection sample, with 5 × 10-4mmol Pd(dba)2、10-4mmol
The solution that the fluorescent sensing material of embodiment 2 preparation and 10mL acetonitrile are mixed to get detects sample as second,
With 5 × 10-4mmol Pd(OAc)2、10-4The fluorescent sensing material of mmol embodiment 2 preparation and 10mL acetonitrile
The solution being mixed to get is as the 3rd detection sample.
Use fluorescence emission spectrometer respectively to reference to sample, the first detection sample, the second detection sample and the 3rd inspection
The fluorescent emission intensity of test sample detects, and result is as shown in figure 17.Figure 17 is the system of the embodiment of the present invention 2
The fluorescent sensing material obtained is fluorescent emission intensity block diagram in the solution containing different palladium materials, and in figure, 1 is ginseng
In the same old way, 2 be the first detection sample, 3 be the second detection sample, 4 be the 3rd detection sample.
As seen in Figure 17, the fluorescent emission intensity of 2,3 and 4 is significantly lower than 1, illustrates that embodiment 2 is made
The fluorescent sensing material obtained all can occur the phenomenon that fluorescence intensity reduces in the presence of zeroth order palladium or divalent palladium,
The fluorescence sense that embodiment 2 prepares can be used in the detection of zeroth order palladium or divalent palladium.
Embodiment 18
Different metal ion pair embodiment 3 prepared fluorescent sensing material UV absorption intensity and fluorescent emission
The impact experiment of intensity
Respectively by 5 × 10-4The PtCl of mmol2、HgCl2、ZnCl2、SnCl2、RuCl3、PbCl2、NiCl2、
NaCl、MgCl2、LiCl、KCl、FeCl3、CuCl2、CoCl2、CdCl2、CaCl2、BaCl2With 10-4
Fluorescent sensing material that mmol embodiment 3 prepares and the mixing of 10mL acetonitrile, detect its UV absorption intensity and
Fluorescent emission intensity, fluorescent emission excitation wavelength is 360nm, and result is as shown in Figure 18 and Figure 19.Figure 18
It is the prepared fluorescent sensing material of the embodiment of the present invention 3 and different metal ion UV absorption in acetonitrile
Spectrogram.Figure 19 be the fluorescent sensing material for preparing of the embodiment of the present invention 3 with different metal ion in acetonitrile
Fluorescent emission spectrogram.
As shown in Figure 18, the fluorescent sensing material that embodiment 3 prepares is without the ultraviolet in the presence of metal ion
Absorption does not has significant change.It appears from figure 19 that at Pd2+In the presence of ion, the fluorescence that embodiment 3 prepares passes
The fluorescent emission intensity of acetonitrile solution of sense material has and significantly weakens；In the presence of other metal ions, real
The fluorescent emission intensity of the acetonitrile solution executing the fluorescent sensing material that example 3 prepares slightly strengthens.Embodiment is described
3 fluorescent sensing materials prepared are to Pd2+The identification of ion has good selectivity.
Embodiment 19
The impact experiment on the fluorescent sensing material fluorescent emission intensity that embodiment 3 prepares of the different palladium class materials
With 10-4The solution that the fluorescent sensing material of mmol embodiment 3 preparation and 10mL acetonitrile are mixed to get is made
For with reference to sample, with 5 × 10-4mmol PdCl2、10-4The fluorescent sensing material and 10 of mmol embodiment 3 preparation
The solution that mL acetonitrile is mixed to get is as the first detection sample, with 5 × 10-4mmol Pd(dba)2、10-4mmol
The solution that the fluorescent sensing material of embodiment 3 preparation and 10mL acetonitrile are mixed to get detects sample as second,
With 5 × 10-4mmol Pd(OAc)2、10-4The fluorescent sensing material of mmol embodiment 3 preparation and 10mL acetonitrile
The solution being mixed to get is as the 3rd detection sample.
Use fluorescence emission spectrometer respectively to reference to sample, the first detection sample, the second detection sample and the 3rd inspection
The fluorescent emission intensity of test sample detects, and result is as shown in figure 20.Figure 20 is the system of the embodiment of the present invention 3
The fluorescent sensing material obtained is fluorescent emission intensity block diagram in the solution containing different palladium materials, and in figure, 1 is ginseng
In the same old way, 2 be the first detection sample, 3 be the second detection sample, 4 be the 3rd detection sample.
As seen in Figure 20, the fluorescent emission intensity of 2,3 and 4 is significantly lower than 1, illustrates that embodiment 3 is made
The fluorescent sensing material obtained all can occur the phenomenon that fluorescence intensity reduces in the presence of zeroth order palladium or divalent palladium,
The fluorescence sense that embodiment 3 prepares 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 is noted that general for the art
For logical technical staff, under the premise without departing from the principles of the invention, it is also possible to make some improvement and profit
Decorations, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a fluorescent sensing material, has formula (I) structure:
Wherein, R1、R2And R3Independently selected from hydrogen, alkyl or alkoxyl.
Fluorescent sensing material the most according to claim 1, it is characterised in that described R1、R2With
R3Independently selected from hydrogen, C1～C10Alkyl or C1～C10Alkoxyl.
Fluorescent sensing material the most according to claim 1, it is characterised in that described R1、R2With
R3Identical.
4. a preparation method for fluorescent sensing material, comprises the following steps:
A), mono-cyclic aromatic aldehyde, 2-cyanopyrimidine and ammonium salt mix in a solvent, the mixture being mixed to get enters
Row heating, obtains the fluorescent sensing material of structure shown in formula (I)；
Wherein, R1、R2And R3Independently selected from hydrogen, alkyl or alkoxyl；
Described mono-cyclic aromatic aldehyde is benzaldehyde, to the one in alkylbenzaldehyde and p-alkoxybenzaldehydes or
Multiple.
Preparation method the most according to claim 4, it is characterised in that described mono-cyclic aromatic aldehyde is benzene
Formaldehyde, to alkylbenzaldehyde or p-alkoxybenzaldehydes.
Preparation method the most according to claim 4, it is characterised in that described ammonium salt be ammonium acetate,
One or more in ammonium chloride, ammonium nitrate, ammonium sulfate and ammonium carbonate.
Preparation method the most according to claim 4, it is characterised in that described 2-cyanopyrimidine, list
The mol ratio of ring aromatic aldehyde and ammonium salt is 1:1～4:2～6.
8. according to the preparation method shown in claim 4, it is characterised in that the temperature of described heating is
70～120 DEG C.
9. according to the preparation method shown in claim 4, it is characterised in that the mode of described heating is micro-
Amplitude is shone.
10. a detection method for palladium class material, comprises the following steps:
By fluorescent sensing material, testing sample and solvent mixing, detection described in any one of claims 1 to 3
The fluorescence intensity of gained mixture；
Described fluorescent sensing material and described solvent are mixed, the fluorescence intensity of detection gained solution；
If the fluorescence intensity of gained mixture is less than the fluorescence intensity of gained solution, in the most described testing sample
Containing zeroth order palladium and/or divalent palladium, without zeroth order palladium and/or divalent palladium in the most described testing sample.
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