CN106867516A - A kind of cadmium ion fluorescent probe based on pyrene exciplex and its preparation method and application - Google Patents
A kind of cadmium ion fluorescent probe based on pyrene exciplex and its preparation method and application Download PDFInfo
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- CN106867516A CN106867516A CN201510923691.7A CN201510923691A CN106867516A CN 106867516 A CN106867516 A CN 106867516A CN 201510923691 A CN201510923691 A CN 201510923691A CN 106867516 A CN106867516 A CN 106867516A
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Abstract
The invention provides a kind of cadmium ion fluorescent probe based on pyrene exciplex and its preparation method and application, the structure of the probe is：Its synthesis step is：1- amino pyrenes are dissolved in CH2Cl2DMAP is added, under condition of ice bath, chloracetyl chloride is slowly added dropwise thereto.It is slowly increased to room temperature reaction and terminates rear rotary evaporation to fall solvent, crosses silicagel column；1- (2- chloracetyls) pyrene, adds acetonitrile, adds KI and DIPEA, and DPA is slowly added dropwise thereto.Back flow reaction, after reaction terminates, is spin-dried for solvent, crosses silicagel column.The present invention realizes fluorescence response signal of the probe to the selectivity of cadmium ion, can be used in the detection of cadmium ion in environment.
Description
Technical field
The invention belongs to chemical analysis detection field, and in particular to a kind of cadmium ion based on pyrene exciplex
Fluorescence probe, its preparation method and application.
Background technology
Cadmium is one of a kind of most dangerous to human body and environment and toxic action metal.In nature, cadmium
Ion is absorbed by various animals and plants and enters human body by food chain enrichment, causes a series of to healthy
Adverse effect.Although cadmium ion has undesirable effect to environment and health, it is still extensive
It is applied in industrial processes.Therefore seek fast and efficiently cadmium ion detection method, be applied to it
The fields such as medicine, environment, food are very necessary.Fluorescence detection method is easy, and sensitivity,
The aspects such as selectivity, response time and biologic applications have outstanding advantages.In recent years, it is used widely.
At present, most of cadmium ion fluorescent probes reported be mainly based upon EDTA amide derivatives be with
Body or DPEA/DPA are the cadmium ion probe of part, by being complexed with cadmium ion after there is being quenched or increasing for fluorescence
By force, or fluorescence emission wavelengths red shift or blue shift realize detection cadmium ion [(a) Gunnlaugsson, T.；Lee,
T.C.；Parkesh,R.Org.Lett.2003,5,4065.(b)Yang,Y.-Y.；Cheng,T.-Y.；Zhu,W.-P.；
Xu,Y.-F.；Qian,X.-H.Org.Lett.2011,13,264.(c)Taki,M.；Desaki,M.；Ojida,A.；
Iyoshi,S.；Hirayama,T.；Hamachi,I.；Yamamoto,Y.J.Am.Chem.Soc.2008,130,
12564.(d)Liu,Z.P.；Zhang,C.L.；He,W.J.；Yang,Z.H.；Gao,X.；Guo,Z.J.Chem.
Commun.2010,46,6138.].These cadmium ion probes generally have preferable sensitivity and quickly ring
Between seasonable, but it is poor to the combination selectivity ratios of cadmium ion, easily it is particularly together by other metal ions
The interference of race's metal zinc ion.It is of the present invention this kind of to be solved well based on pyrene exciplex probe
Selective problems.
The content of the invention
It is an object of the invention to provide a kind of cadmium ion fluorescent probe based on pyrene exciplex, its preparation side
Method and application, the probe have single-minded fluorescence response signal and sensitivity higher, preparation side to cadmium ion
Method is simple, is adapted to amplify synthesis and practical application.
The invention provides a kind of cadmium ion fluorescent probe based on pyrene exciplex, the fluorescence probe structure
It is as follows：
The present invention provides the preparation method of the cadmium ion fluorescent probe based on pyrene exciplex, and the method is specific
Step is as follows：
1) synthesis of 1- (2- chloracetyls) pyrene：1- amino pyrene adds CH2Cl2In, DMAP is added,
Under condition of ice bath, chloracetyl chloride is slowly added dropwise thereto.It is slowly increased to room temperature, stirring reaction 5-8h.Reaction
Rotary evaporation falls solvent after end, crosses silica gel post separation, eluent petroleum ether:Ethyl acetate=
100:5-100:20；The eluant, eluent containing product for being spin-dried for being collected into obtains 1- (2- chloracetyls) pyrene.2) probe
Synthesis：1- (2- chloracetyls) pyrene adds acetonitrile as solvent, adds KI and DIPEA, thereto slowly
DPA is added dropwise.80-120 DEG C of back flow reaction 8-14h, after reaction terminates, is spin-dried for solvent, crosses silica gel post separation,
Eluant dichloromethane:Methyl alcohol=200:1-100:10；The eluant, eluent containing product for being spin-dried for being collected into obtains right
Probe shown in claim 1.Step 1) in, 1- amino pyrenes:CH2Cl2:DMAP:Chloracetyl chloride=1g:
20-80mL:0.7-1mL:0.4-0.5mL。
Step 2) in, 1- (2- chloracetyls) pyrene:Acetonitrile:KI:DIPEA:DPA=1g:20-80mL:
0.5-0.6g:8-12mL:2.4-2.8mL。
Step 1) in, at 15-40 DEG C, flow velocity is 0.1mL/min -20 to the silicagel column separation temperature
ML/min, eluant, eluent is dichloromethane:Methyl alcohol=200:1-100:10, it is collected into and contains 1- (2- chloracetyls)
30-60 DEG C is spin-dried under the eluant, eluent low pressure of pyrene.
Step 2) in, the silica gel post separation, at 15-40 DEG C, flow velocity is 0.1mL/min -20 to temperature
ML/min, eluant, eluent is dichloromethane:Methyl alcohol=200:0-100:10, it is collected into and contains 1- (2- chloracetyls)
30-60 DEG C is spin-dried under the eluant, eluent low pressure of pyrene.
The fluorescence probe that the present invention is provided is applied to detect the cadmium ion in the aqueous solution in environmental protection.
The present invention has feature in detail below：
Probe molecule raw material is easy to get, and synthetic route is simple, reaction condition is gentle, post processing is simple and convenient, right
Cadmium ion has special recognition capability, and response speed is very fast, acid amides-DPA acceptors and the 2 of cadmium ion:1 knot
Conjunction mode, causing the fluorescence peak of exciplex strengthens.Probe is in 5%CH3It is molten in the water mixed solution of CN
Preferably, in 380nm, with the addition of cadmium ion, probe molecule goes out Monomer emission wavelength solution property in 490nm
Now stronger exiplex emission peak.Therefore can be used for detecting the cadmium ion in the aqueous solution, can be applicable to
The detection of cadmium ion in the middle of environment.
Brief description of the drawings
Fig. 1 is the structural formula of the fluorescence probe；
Fig. 2 is the synthetic route schematic diagram of the fluorescence probe；
Fig. 3 is intermediate 1- (2- chloracetyls) pyrene prepared by embodiment 11H NMR spectras
Fig. 4 is intermediate 1- (2- chloracetyls) pyrene prepared by embodiment 113C NMR spectras
Fig. 5 is fluorescence probe prepared by embodiment 11H NMR spectras
Fig. 6 is fluorescence probe prepared by embodiment 113C NMR spectras
Fig. 7 is in 5%CH3The aqueous solution middle probe of CN adds Cd2+Front and rear fluorescence spectra；
Fig. 8 is that fluorescence probe prepared by embodiment 1 adds the fluorescence spectra change feelings after different metal ions
Condition；
Fig. 9 is J-P curves, and probe prepared by embodiment 1 is 10 μm, horizontal seat with the concentration summation of cadmium ion
Be designated as the concentration of probe from 0 μM -10 μM, ordinate 490nm exciplex fluorescence peak intensities with it is maximum
The ratio of intensity；
Figure 10 nuclear-magnetisms are titrated, and solvent for use is CD3CN, the initial concentration of probe is 0.5mg/mL, Xiang Qi
The Cd of middle titration various concentrations2+The nuclear magnetic spectrogram of ion；
Specific embodiment
The following examples will be further described to the present invention, but not thereby limiting the invention.
Embodiment 1：Exciplex type cadmium ion fluorescent probe, basic building-up process is as follows：
1) synthesis of 1- (2- chloracetyls) pyrene：The 1- amino pyrenes of 1g are added in single port bottle, 100mL is added
CH2Cl2As solvent, the DMAP of 0.9g is added, under condition of ice bath, 0.43 is slowly added dropwise thereto
The chloracetyl chloride of mL.Room temperature is slowly increased to, 6h is stirred.Reaction terminates rear rotary evaporation and falls solvent, crosses silicon
Glue post, eluent petroleum ether：Ethyl acetate=10:1.It is spin-dried for being collected into the eluant, eluent containing product, produces
Thing is white solid, yield 74%.Intermediate nucleus magnetic hydrogen spectrum, carbon spectrum difference are as shown in Figure 3, Figure 4.
2) synthesis of probe：0.63g 1- (2- chloracetyls) pyrene is added in single port bottle, adds 150mL's
Acetonitrile adds the DIPEA of the KI and 6mL of 0.38g as solvent, and 1.6mL is slowly added dropwise thereto
DPA.80 DEG C of back flow reaction 12h, after reaction terminates, are spin-dried for solvent, cross silicagel column, and eluant, eluent is
CH2Cl2, it is spin-dried for being collected into the eluant, eluent containing product, product is yellow oil, yield 70%.It is glimmering
Light probe nucleus magnetic hydrogen spectrum, carbon spectrum difference are as shown in Figure 5, Figure 6.
The hydrogen modal data of probe is as follows：1H NMR(CD3CN,400MHz)δ11.47(s,1H),8.65(t,3H),
8.51(d,2H),8.25(m,4H),8.09(m,3H),7.70(t,2H),7.45(d,2H),7.21(t,2H),4.09(s,
4H),3.66(s,2H)。
Embodiment 2：The response condition that fluorescence probe prepared by embodiment 1 is determined to cadmium ion
Probe prepared by embodiment 1 is dissolved in CH3In CN solution, CH is added to3CN:H2O(1:19, v/v)
In mixed solvent, it is 10 that system is made into concentration and probe concentration-5The solution of M, tests the change of its fluorescence spectrum.
Fig. 7 middle probes concentration is 10 μM, and when the concentration of cadmium ion is 5 μM, its fluorescence spectrum is 490
Change is remarkably reinforced at nm, shows two molecular probes and a cadmium ion with 2:After 1 mode is combined,
Two pyrene fluorogens are close to and generate exciplex fluorescence peak.Its excitation wavelength is 360nm.
Embodiment 3：Fluorescence probe prepared by embodiment 1 is with cadmium ion in CH3Complexing ratio in CN solution
The CH that probe prepared by embodiment 1 is dissolved in3In CN solution, it is 10 that system is made into concentration and probe concentration-5M's
Solution, test probe changes with the fluorescence spectrum after different metal ions complexing.The metal ion for being added is
The 3eq of concentration and probe concentration, respectively containing Zn2+, Fe3+, Cr3+, Ni2+, Co2+, Pd2+, Ag+, Cu2+,
Hg2+, Mn2+, Cu+, Fe2+, Cd2+, Na+, Pb2+, Ca2+, Pt2+, Mg2+, K+Perchlorate is water-soluble
Liquid.Result is as shown in figure 8, show to add excessive Cd2+, probe and Cd can be made2+Form 1:1 complexing,
Cause that monomer fluorescence peak is a certain degree of to be quenched.
It is 10 μM with the concentration summation of cadmium ion to keep probe, in CH3CN：H2O=5:95 (v/v) are molten
[probe]/[probe+Cd is respectively configured in agent2+]=0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,
0.9th, 1 solution, tests its fluorescence spectrum, and the fluorescence intensity level gone at the 495nm of exciplex is J-P
Curve, the concentration of probe from 0 μM -10 μM, as a result as shown in figure 9, abscissa represents that probe is total with concentration
The ratio of sum, ordinate is the ratio of 490nm exciplexs peak intensity and maximum fluorescence intensity, linearly
Fitting focus takes maximum at 6.6, illustrate that now exciplex fluorescence peak is most strong, now probe and cadmium from
Son is 2:1 complexing.
Embodiment 4：Fluorescence probe prepared by embodiment 1 is in CD3The nuclear-magnetism being complexed with cadmium ion in CN is titrated
In CD3In CN, concentration and probe concentration prepared by embodiment 1 is 0.5mg/mL, and different working as is added dropwise thereto
The Cd of amount2+, nucleus magnetic hydrogen spectrum is done respectively.As shown in Figure 10, nuclear magnetic spectrogram is from top to bottom as addition 0 for result
The cadmium ion probe of eq, 0.2eq, 0.4eq, 0.5eq, 0.6eq, 0.8eq, 1eq, 1.2eq, 1.4eq
With Cd2+Ion.Result shows probe and Cd2+Mol ratio is 2:When 1, the complex compound of stabilization can be formed, after
It is continuous that Cd is added dropwise2+When, complexing mode changes into 1:1 form, Cd2+Stable comple is formed when excessive again,
It 2:1 complexing and 1:The form complexed of 1 complexing is different from nucleus magnetic hydrogen spectrum.
Claims (7)
1. a kind of cadmium ion fluorescent probe based on pyrene exciplex, it is characterised in that：The fluorescence probe knot
Structure is as follows：
2. the preparation method of the cadmium ion fluorescent probe based on pyrene exciplex described in a kind of claim 1,
It is characterized in that：Comprise the following steps that：
1) synthesis of 1- (2- chloracetyls) pyrene：1- amino pyrene adds CH2Cl2In, DMAP is added,
Under condition of ice bath, chloracetyl chloride is slowly added dropwise thereto, be slowly increased to room temperature, stirring reaction 5-8h, reaction
Rotary evaporation falls solvent after end, crosses silica gel post separation, eluent petroleum ether:Ethyl acetate=
100:5-100:20；The eluant, eluent containing product for being spin-dried for being collected into obtains 1- (2- chloracetyls) pyrene；
2) synthesis of probe：1- (2- chloracetyls) pyrene adds acetonitrile as solvent, adds KI and DIPEA,
DPA, 80-120 DEG C of back flow reaction 8-14h are slowly added dropwise thereto, after reaction terminates, solvent is spin-dried for, and cross silicon
Glue post separation, eluant dichloromethane:Methyl alcohol=200:1-100:10；It is spin-dried for the wash-out containing product being collected into
Agent obtains probe shown in claims 1.
3. according to the preparation method described in claim 2, it is characterised in that：Step 1) in, 1- amino pyrenes
CH2Cl2:DMAP:Chloracetyl chloride=1g:20-80mL:0.7-1mL:0.4-0.5mL.
4. according to the preparation method described in claim 2, it is characterised in that：Step 2) in, 1- (2- chloroethenes
Acyl group) pyrene:Acetonitrile:KI:DIPEA:DPA=1g:20-80mL:0.5-0.6g:8-12mL:2.4-2.8
mL。
5. according to the preparation method described in claim 2, it is characterised in that：Step 1) in, the silica gel
At 15-40 DEG C, flow velocity is 0.1mL/min -20mL/min to post separation temperature, and eluant, eluent is dichloromethane:
Methyl alcohol=200:1-100:10, it is collected into 30-60 DEG C of rotation under the eluant, eluent low pressure containing 1- (2- chloracetyls) pyrene
It is dry.
6. according to the preparation method described in claim 2, it is characterised in that：Step 2) in, the silica gel
Post separation, at 15-40 DEG C, flow velocity is 0.1mL/min -20mL/min to temperature, and eluant, eluent is dichloromethane:
Methyl alcohol=200:0-100:10, it is collected into 30-60 DEG C of rotation under the eluant, eluent low pressure containing 1- (2- chloracetyls) pyrene
It is dry.
7. the cadmium ion fluorescent probe based on pyrene exciplex described in a kind of claim 1 is examined in cadmium ion
Application in survey.
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Cited By (3)
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| CN113754555A (en) * | 2021-10-13 | 2021-12-07 | 东北农业大学 | Amido pyrene derivative fluorescent probe and preparation method and application thereof |
| CN114438091A (en) * | 2022-02-08 | 2022-05-06 | 中国科学院生态环境研究中心 | DNA fluorescent probe and method for detecting cadmium ions by using same |
| CN115621465A (en) * | 2022-12-20 | 2023-01-17 | 江苏正力新能电池技术有限公司 | Modified silicon-based negative electrode material, preparation method thereof and lithium ion battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113754555A (en) * | 2021-10-13 | 2021-12-07 | 东北农业大学 | Amido pyrene derivative fluorescent probe and preparation method and application thereof |
| CN114438091A (en) * | 2022-02-08 | 2022-05-06 | 中国科学院生态环境研究中心 | DNA fluorescent probe and method for detecting cadmium ions by using same |
| CN114438091B (en) * | 2022-02-08 | 2023-12-01 | 中国科学院生态环境研究中心 | DNA fluorescent probe and method for detecting cadmium ions by using same |
| CN115621465A (en) * | 2022-12-20 | 2023-01-17 | 江苏正力新能电池技术有限公司 | Modified silicon-based negative electrode material, preparation method thereof and lithium ion battery |
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