CN105273429A - Fluorescent dye and preparation method and application thereof - Google Patents
Fluorescent dye and preparation method and application thereof Download PDFInfo
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- CN105273429A CN105273429A CN201510536336.4A CN201510536336A CN105273429A CN 105273429 A CN105273429 A CN 105273429A CN 201510536336 A CN201510536336 A CN 201510536336A CN 105273429 A CN105273429 A CN 105273429A
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Abstract
The present invention discloses a thiadiazole-group-containing substituted polyacetylene fluorescent dye with the structural formula shown in the specification, the prepared polymer fluorescent dye is simple in synthesis, can be applied to fluorescent sensors, can be used in Pd<2+> and thiophanate-methyl detection by fluorescence assay, has good selectivity and high sensitivity, can be made into a test strip to detect Pd <2+> ions, and is convenient and practical.
Description
Technical field
The present invention relates to a kind of polymer fluorescent dye well its preparation method, specifically a kind of substituted polyacetylene fluorescence dye containing thiadiazoles group and preparation method thereof, this fluorescence dye application in the sensor simultaneously and for detecting palladium ion or thiophanate methyl, belongs to single photon fluorescence sensor field.
Background technology
Fluorescent optical sensor refers to can have an effect with analyte to be measured and by the molecular device changing into signal manifestation of fluorescent signal.Because it has many merits, the advantages such as such as selectivity is good, highly sensitive, fast response time, are widely used in a series of field such as bio-imaging, environmental monitoring.Simply be easy to modify due to structure based on micromolecular fluorescent optical sensor, study more deep.Polymer fluorescent sensor have signal large, be easy to the interest that the advantages such as device cause increasing people in recent years, wherein LARGE CONJUGATE MOLECULES fluorescent optical sensor is especially outstanding.
Summary of the invention
The present invention aims to provide a kind of fluorescence dye and its preparation method and application, the present invention has good selectivity containing the substituted polyacetylene fluorescent optical sensor of thiadiazoles group, sensitivity is very high, can by the mode sequence detection palladium ion of fluorescence and thiophanate methyl, and the test paper that can detect palladium ion can be made, easy to use.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is:
A kind of fluorescence dye, be the substituted polyacetylene containing thiadiazoles group, its structural formula is:
In formula, x is 0.36, y is 0.64.
Described a kind of fluorescence dye, is applied to fluorescent optical sensor.
Described a kind of fluorescence dye, for detecting palladium ion and thiophanate methyl.
A preparation method for described fluorescence dye, comprises the following steps:
(1) be take iodobenzene, 5-chloro-1-pentyne, Pd (PPh at 1: 1: 0.02: 0.05: 10 by amount ratio
3) Cl
2, CuI, Et
3n, when anhydrous and oxygen-free by iodobenzene, the chloro-1-pentyne of 5-, Pd (PPh
3) Cl
2, CuI joins Et
3in N, at 80 DEG C, react 12h.After reaction, be spin-dried for reaction solution, with dichloromethane extraction, obtain organic layer.Again by purification by silica gel column chromatography, obtain intermediate
3;
(2) be take intermediate at 3: 0.15: 0.15: 8 by amount of substance ratio
3, catalyzer WCl
6and SnPh
4, toluene, intermediate 3 and catalyzer to be dissolved respectively in toluene, stir-activating 1h at 80 DEG C, then by intermediate
3solution is transferred in catalyst solution and reacts 2 days in 80 DEG C; After reaction terminates, dropwise instillation is not less than sedimentation in the methyl alcohol of 100 times of toluene amount, obtains intermediate
p0.
(3) be take intermediate at 1: 2: 5: 0.2: 10 by amount ratio
p0,5-methyl-2-sulfydryl-1,3,4 thiadiazoles, K
2cO
3, KI, THF, by intermediate P0,5-methyl-2-sulfydryl-1,3,4 thiadiazoles, K
2cO
3, KI joins in THF respectively, reflux 24h at 75 DEG C.After reaction terminates, reaction solution is dropwise added drop-wise to sedimentation in methyl alcohol, obtains target product
p1.
The preparation method of described fluorescence dye, in step (1), purification by silica gel column chromatography adopts ethyl acetate: sherwood oil is 1:15.
The preparation method of described fluorescence dye, reaction and the operation of each step all adopt Schlenk technology to carry out under dry argon gas atmosphere, and the purification of polymkeric substance is carried out in air atmosphere.
The making method of described fluorescence dye test paper, comprises the following steps: by fluorescent sensing material
p1be dissolved in tetrahydrofuran (THF), concentration is 1 × 10
-5mol/L; Test strip is immersed in its solution to take out after 1min after solution evaporation completes and just completes.
Compared with the prior art, beneficial effect of the present invention is embodied in:
Fluorescence dye synthesis prepared by the present invention is simple, structure obtains nuclear-magnetism, infrared sign confirms, there is higher fluorescence quantum yield, highly sensitive, highly selective can realize to detecting palladium ion and thiophanate methyl sequence detection in homogeneous system, particularly also can be made into test paper, be conveniently applied to the detection of palladium ion.
Accompanying drawing explanation
Fig. 1 is fluorescence dye
p1make test paper to Pd
2+ion fluorescence response photo;
Fig. 2 (a) is Pd
2+ion titration
p1tHF solution fluorescence Strength Changes figure;
Fig. 2 (b) is the fluorescence intensity change figure that common positively charged ion disturbs titration;
Fig. 2 (c) is
p1to the selectivity photo of different metal ion;
Fig. 3 (a) be thiophanate methyl (
tM) titration
p1/ Pd
2+change in fluorescence figure during mixture;
Fig. 3 (b) is the fluorescence intensity change figure that common agricultural chemicals disturbs titration;
Fig. 3 (c) is
p1/ Pd
2+mixture is to the selectivity photo of different agricultural chemicals.
Embodiment
Below in conjunction with embodiment, the present invention is described in further details.
Polyacetylene, as one of the most classical conjugated polymers, is used to make solar cell, semiconductor material and electroactive polymer.But polyacetylene has and insolublely not to melt, the shortcoming such as oxidizable, and substituted polyacetylene well overcomes these shortcomings, has well steady some property and processing characteristics, is widely used in liquid crystal material field, also accidental for polymer fluorescent sensor field.Thiadiazoles group is a good recognition group, has multiple transition ion hapto.Thiadiazoles group is introduced and is replaced the macromole fluorescent optical sensor of alkynes carcasing containing the substituted polyacetylene of thiadiazolyl group by we for this reason.As everyone knows, palladium ion and nitrogen, sulphur have good coordination ability, thus we with this polymer fluorescent sensor detect palladium ion, simultaneously with one contain more nitrogen, sulphur atom thiophanate methyl (
tM) palladium ion is seized, therefore realize to palladium ion and thiophanate methyl (
tM) sequence detection.
Synthetic route of the present invention is as follows:
。
Embodiment 1:
1, intermediate
3synthesis
When anhydrous and oxygen-free by iodobenzene 0.204g (1mmol), 5-chloro-1-pentyne 0.1025g (1mmol), Pd (PPh
3) Cl
20.014g (0.02mmol), CuI0.0095g (0.05mmol) join Et
3in N (10mL), at 80 DEG C, react 12h.After reaction terminates, filter, be spin-dried for reaction solution, with dichloromethane extraction, obtain organic layer.Again by 200-300 order purification by silica gel column chromatography, elutriant is ethyl acetate: sherwood oil=1:10.Obtain the intermediate of colourless transparent liquid
3(0.1451g), productive rate is 84%.
2, intermediate
p0synthesis
Reaction and the operation of each step all adopt Schlenk technology to carry out under dry argon gas atmosphere, and the purification of polymkeric substance is carried out in air atmosphere.All operations all carries out under argon shield atmosphere, 1g intermediate
3with catalyzer WCl
6, SnPh
4(catalyzer WCl is dissolved respectively in the toluene of 8mL
6, SnPh
4amount be respectively 59mg and 63mg), stir-activating 1h at 80 DEG C, then by intermediate
3solution is transferred in catalyst solution and reacts 2 days in 80 DEG C.After reaction terminates, sedimentation in the methyl alcohol of dropwise instillation a large amount of (more than 20 times of reaction solution volume), obtain faint yellow target product 0.602g, productive rate is 60.2%.Referred to as
p0.
1HNMR(400MHz,CDCl
3,δ,ppm):8.02-6.05(ArH),3.62-0.61(-CH
2-).
13CNMR(600MHz,CDCl
3):δ,ppm,144.62-134.56,132.71-1.22.32,47.56-42.34,36.51-26.72
FT-IR(KBr,cm
?1):2969.20,1644.81,1481.60,1436.78,1377.25,1254.84,1179.93,1072.24,800.66,692.97.
3, target product
p1synthesis
By intermediate
p089mg (0.5mmol), 5-methyl-2-sulfydryl-1,3,4 thiadiazoles 132.2mg (1mmol), K
2cO
3690mg (2.5mmol), KI33mg (0.2mmol) join in 10mLTHF respectively, and reflux 24h at 75 DEG C.After reaction terminates, reaction solution is dropwise added drop-wise to sedimentation in methyl alcohol, obtains faint yellow product 0.071g, productive rate 73%, referred to as
p1, structural formula is as follows:
1HNMR(400MHz,CDCl
3,δ,ppm):8.11-6.12(ArH),3.60-2.84(-CH
2-),2.84-2.01(-CH
3),2.01-0.34(-CH
2-).
13CNMR(600MHz,CDCl
3,δ,ppm,):166.1-165.1,165.1-163.3,144.1-136.4,130.9-122.0,36.1-32.5,15.6
FT-IR(KBr,cm
?1):2961.81,1579.92,1488.29,1429.41,1305.01,1026.08,
974.58,761.82,696.32.
Embodiment 2: the exploration and application of test paper
By fluorescent sensing material
p1be dissolved in tetrahydrofuran (THF), concentration is 1 × 10
-5mol/L.Test strip is immersed in its solution to take out after 1min after solution evaporation completes and just completes.Test strip is immersed in the Pd of different concns
2+solution in, soak 1min, take out dry after, just can to Pd under hand-held ultraviolet lamp 356nm wave band
2+detect.
By fluorescence dye
p1the test paper made is simultaneously to Pd
2+ion detects, and test paper is to Pd
2+ion fluorescence responds as shown in Figure 1,
A) blank, B)
p1, C)
p1+ Pd
2+pd
2+ionic concn is 0.5 × 10
-5mol/L, D)
p1+ Pd
2+pd
2+ionic concn is 1.0 × 10
-5mol/L, E)
p1+ Pd
2+pd
2+ionic concn is 1.5 × 10
-5mol/L, visible test paper can detect Pd
2+ion.
Embodiment 3: to Pd under solution state (homogeneous phase)
2+the detection of ion
As shown in Figure 2 (a) shows, Pd
2+ion titration
p1tHF solution,
p1concentration is 4 × 10
-6mol/L, works as Pd
2+ionic concn is 2.5 × 10
-7during mol/L, fluorescence just starts cancellation, and cancellation can reach 94%.Solution colour is without considerable change simultaneously, and other common positively charged ions do not disturb it, as shown in Fig. 2 (b).1:
p1only, 2:Pd
2+, 3:Al
3+, 4:Au
3+, 5:Ba
2+, 6:Fe
3+, 7:Ni
2+, 8:Mg
2+, 9:Ce
3+, 10:Cr
3+, 11:Cs
+, 12:Ag
+, 13:Au
+, 14:Zn
2+, 15:Cu
2+, 20:Hg
2+(each ionic concn is 2.0 × 10
-5mol/L).To the selectivity photo of different metal ion as shown in Figure 2 (c).
Therefore
p1pd can be detected by fluorescence mode
2+ion.Excitation wavelength 324nm, slit width is 10nm.
Embodiment 4:
p1/ Pd
2+combined probe to thiophanate methyl (
tM) detection
As shown in Fig. 3 (a), thiophanate methyl (
tM) titration
p1/ Pd
2+mixture,
p1concentration is 4 × 10
-6mol/L, Pd
2+ionic concn is 6 × 10
-6mol/L, when thiophanate methyl (
tM) concentration is 2 × 10
-6during mol/L, fluorescence starts to recover, and final recovery can reach 92% of green strength.Solution colour is without considerable change, and other common agricultural chemicals do not disturb it, as shown in Figure 3 (b).1:
p1, 2:Pd
2+, 3: thiophanate methyl, 4: Y 3,5: prometryn, 6: tetramethyl-thiuram disulfide, 7: metsulfuronmethyl, 8: methomyl, 9: glyphosate.(each pesticide concentration is 9 × 10
-5mol/L).To the selectivity photo of different agricultural chemicals as shown in Figure 3 (c).
Therefore
p1also can by the mode of fluorescence detect thiophanate methyl (
tM).Excitation wavelength 324nm, slit width is 10nm.
Claims (7)
1. a fluorescence dye, has following general structure P1:
In formula, x is 0.36, y is 0.64.
2. a kind of fluorescence dye as claimed in claim 1, is characterized in that: be applied to fluorescent optical sensor.
3. a kind of fluorescence dye as claimed in claim 2, is characterized in that: for detecting palladium ion and thiophanate methyl.
4. a preparation method for fluorescence dye described in claim 1, is characterized in that comprising the following steps:
(1) be take iodobenzene, 5-chloro-1-pentyne, Pd (PPh at 1: 1: 0.02: 0.05: 10 by amount ratio
3) Cl
2, CuI, Et
3n, when anhydrous and oxygen-free by iodobenzene, the chloro-1-pentyne of 5-, Pd (PPh
3) Cl
2, CuI joins Et
3in N, at 80 DEG C, react 12h; After reaction, be spin-dried for reaction solution, with dichloromethane extraction, obtain organic layer; Again by purification by silica gel column chromatography, obtain intermediate
3;
(2) be take intermediate at 3: 0.15: 0.15: 8 by amount of substance ratio
3, catalyzer WCl
6and SnPh
4, toluene, intermediate 3 and catalyzer to be dissolved respectively in toluene, stir-activating 1h at 80 DEG C, then by intermediate
3solution is transferred in catalyst solution and reacts 2 days in 80 DEG C; After reaction terminates, dropwise instillation is not less than sedimentation in the methyl alcohol of 100 times of toluene amount, obtains intermediate
p0;
(3) be take intermediate at 1: 2: 5: 0.2: 10 by amount ratio
p0,5-methyl-2-sulfydryl-1,3,4 thiadiazoles, K
2cO
3, KI, THF, by intermediate P0,5-methyl-2-sulfydryl-1,3,4 thiadiazoles, K
2cO
3, KI joins in THF respectively, reflux 24h at 75 DEG C; After reaction terminates, reaction solution is dropwise added drop-wise to sedimentation in methyl alcohol, obtains target product
p1.
5. the preparation method of fluorescence dye described in a kind of claim 1 as claimed in claim 4, is characterized in that: in step (1), purification by silica gel column chromatography adopts ethyl acetate: sherwood oil is 1:15.
6. the preparation method of fluorescence dye described in a kind of claim 1 as claimed in claim 4, is characterized in that: reaction and the operation of each step all adopt Schlenk technology to carry out under dry argon gas atmosphere, and the purification of polymkeric substance is carried out in air atmosphere.
7. the making method containing fluorescence dye test paper described in claim 1, is characterized in that comprising the following steps: by fluorescent sensing material
p1be dissolved in tetrahydrofuran (THF), concentration is 1 × 10
-5mol/L; Test strip is immersed in its solution to take out after 1min after solution evaporation completes and just completes.
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2015
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| JPH04248818A (en) * | 1991-01-25 | 1992-09-04 | Asahi Chem Ind Co Ltd | Diacetylene polymer |
| CN1342720A (en) * | 2001-10-16 | 2002-04-03 | 上海交通大学 | Conjugated polymer containing dibenzo-thiophene dioxide and its preparing process |
| CN1597718A (en) * | 2004-08-19 | 2005-03-23 | 复旦大学 | Alcohol soluble polyterephtha acetylene derivative and its preparation method and application |
| CN101381424A (en) * | 2008-10-21 | 2009-03-11 | 武汉大学 | Polyacetylene high molecule containing imidazole side group |
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