CN109762364B - Pyridinium ion modified near-infrared squaric acid dye and preparation and application thereof - Google Patents
Pyridinium ion modified near-infrared squaric acid dye and preparation and application thereof Download PDFInfo
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- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 title claims abstract description 16
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000980 acid dye Substances 0.000 title claims abstract description 11
- 239000005630 Diquat Substances 0.000 claims abstract description 37
- SYJFEGQWDCRVNX-UHFFFAOYSA-N diquat Chemical compound C1=CC=[N+]2CC[N+]3=CC=CC=C3C2=C1 SYJFEGQWDCRVNX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000975 dye Substances 0.000 claims abstract description 35
- 238000001514 detection method Methods 0.000 claims abstract description 13
- IHXWECHPYNPJRR-UHFFFAOYSA-N 3-hydroxycyclobut-2-en-1-one Chemical compound OC1=CC(=O)C1 IHXWECHPYNPJRR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007850 fluorescent dye Substances 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 35
- 238000010992 reflux Methods 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- -1 (1) pyridinium ion-modified trimethylindoline Chemical class 0.000 claims description 24
- 238000010898 silica gel chromatography Methods 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
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- 239000012043 crude product Substances 0.000 claims description 12
- 239000003480 eluent Substances 0.000 claims description 12
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- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000001308 synthesis method Methods 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- FLHJIAFUWHPJRT-UHFFFAOYSA-N 2,3,3-trimethylindole Chemical compound C1=CC=C2C(C)(C)C(C)=NC2=C1 FLHJIAFUWHPJRT-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
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- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 3
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
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- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 8
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 8
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- 229910021645 metal ion Inorganic materials 0.000 description 3
- MCIDGHHVKNZHRD-UHFFFAOYSA-N 1,2,2-trimethyl-3h-indole Chemical class C1=CC=C2CC(C)(C)N(C)C2=C1 MCIDGHHVKNZHRD-UHFFFAOYSA-N 0.000 description 2
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid Chemical compound CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 description 2
- PWVXXGRKLHYWKM-UHFFFAOYSA-N 5-[2-(benzenesulfonyl)ethyl]-3-[(1-methylpyrrolidin-2-yl)methyl]-1h-indole Chemical compound CN1CCCC1CC(C1=C2)=CNC1=CC=C2CCS(=O)(=O)C1=CC=CC=C1 PWVXXGRKLHYWKM-UHFFFAOYSA-N 0.000 description 2
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- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- DARPYRSDRJYGIF-PTNGSMBKSA-N (Z)-3-ethoxy-2-naphthalen-2-ylsulfonylprop-2-enenitrile Chemical compound C1=CC=CC2=CC(S(=O)(=O)C(\C#N)=C/OCC)=CC=C21 DARPYRSDRJYGIF-PTNGSMBKSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a pyridinium ion modified near-infrared squaric acid dye and a preparation method and application thereof. The near-infrared squarylium dye has good stability and excellent optical performance, and particularly, the water solubility of the dye can be enhanced by a pyridinium ion group. When the near-infrared squaraine dye is used for detecting the diquat, diquat molecules can interact with the dye molecules to trigger the change of a dye absorption spectrum and a fluorescence spectrum, so that the dye can be used as a fluorescent probe for detecting the diquat and used for detecting the fluorescence of the diquat in the environment, and has better detection sensitivity.
Description
Technical Field
The invention belongs to the field of analytical chemistry, and particularly relates to a pyridinium ion modified near-infrared squarylium dye, a preparation method thereof and application thereof in fluorescence detection of diquat in the environment.
Background
Diquat (1, 1 '-ethylene-2, 2' -bipyridyl dibromide salt, DQ) is a non-selective contact herbicide similar to Paraquat (PQ), and is widely used in agriculture and horticulture due to its advantages of being cheap, rapid and effective. With the development of economy, people pay more and more attention to food safety, and the risk potential of the crop growth environment gradually becomes a focus. In recent years, DQ has been classified as a moderately toxic pesticide by the world health organization, has moderate irritation to eyes and skin of mammals, has a great influence on the redox activity of organisms after being taken, and has certain damage to the functions of body organs such as heart, lung, liver, kidney and the like. It is often encountered in the case of accidental and suicide poisoning, together with paraquat. Due to its high clinical and environmental relevance, it is of great significance to develop effective DQ detection methods.
At present, there have been reports of high performance liquid chromatography (Yushidong, Wusong, Zhengmin, Chenzhongxiang, Zhaojiwei, Mulibre, high performance liquid chromatography for measuring paraquat and diquat in fishery waters, analytical laboratories, 2013, 32 (2): 54-57; Chenjing, Liuhuan, Anbao, Luyan, schooling, on-line purification/solid phase extraction-high performance liquid chromatography for measuring paraquat and diquat in drinking water and environmental water, chromatography, 2012, 30 (10): 1068-, zheng jiao, nixi Shi, Song Yang, Liujunting, ultraviolet spectrophotometry for measuring diquat in urine, journal of Chinese forensic science 2014 (6): 551-552; research progress of a Zhu-Yu field, Li jin-could, Gao-Sujun, Zheng Yan-Yan and a near infrared spectrum technology in the field of edible oil rapid detection is disclosed, wherein the research progress is as follows, Chinese oil and fat, 2017, and 42 (7): 140-143; m. Almeida, M. Yonamine, Gas Chromatography-quantitative method for the determination of the secretion para-source and lipid in plants and extracts, Journal of Chromatography B, 2007, 853(1-2): 260-; gaolina, Song Yang, Juan, Liujunting, solid phase microextraction combined with air chromatography for measuring diurethane in blood plasma, journal of Chinese Law medicine, 2014, 29 (5): 427. -, 430.), spectrophotometry (W. Silagproh, T. Somboonsuk, O. Chailapakul, K. Songsrise, Novel colorimetric assay for para-quality detection of hydrophobic-silica nanoparticles, Talanta, 2017,174: 448-, analytica Chimica Acta, 2001, 427(2):165-171, R, Garcia-Febrero, J. -P, Salvador, F, Sanchez-Baeza, M.P. Marco, Rapid method based on immunological analysis for determination of paraquat reactivity in the animal, barrel and potato, Food Control, 2014, 41: 193-201) and the like. Although these techniques have the advantages of high selectivity and high sensitivity, they also have the disadvantages of instability, and require expensive instruments and time-consuming operations. In contrast, DQ detection and analysis based on the fluorescent probe has the advantages of simplicity, high sensitivity, high selectivity and the like. However, there are few reports of fluorescent chemical sensors for detecting DQ based on molecular recognition.
The squaric acid dye is a 1, 3-disubstituted derivative which is generated by condensation reaction of squaric acid or ester thereof and substances containing electron-rich groups, such as arylamine, phenols or nitrogen-containing heterocyclic compounds, and has strong absorption in a near infrared region. The compounds are characterized by narrow and strong absorption band in the visible light to near infrared region and better light stability. Compared with other organic dyes, the squarylium dye has wider application prospect due to the characteristics of excellent fluorescence emission performance, good optical stability, easy modification and the like.
According to the invention, the structure of the squaric acid dye is optimized, the pyridinium ion modified squaric acid dye is synthesized, the water solubility of the squaric acid dye is enhanced, the application of the squaric acid dye in diquat fluorescence detection is realized, and the method has a good development prospect.
Disclosure of Invention
The invention aims to provide a pyridinium ion modified near-infrared squarylium dye, a preparation method thereof and application thereof in diquat fluorescence detection.
In order to achieve the purpose, the invention adopts the following technical scheme:
a pyridinium ion modified near infrared squarylium dye having the following structural formula:
the preparation method of the pyridinium ion modified near-infrared squarylium dye comprises the following steps:
(1) pyridinium ion-modified trimethylindoline derivative
And dicyanovinylsquaric acid derivatives
Mixing at a molar ratio of 2:1, dissolving in solvent, N2Carrying out reflux reaction under protection;
(2) cooling to room temperature, and removing the solvent under reduced pressure to obtain a crude product;
(3) purifying by silica gel column chromatography to obtain the near-infrared squaric acid dye;
wherein the solvent used in the step (1) is a mixed solution of n-butyl alcohol and toluene according to a volume ratio of 1:1, the reflux temperature is 145 ℃, and the reflux time is 5 hours;
and (3) performing silica gel column chromatography by using a mixed solution of dichloromethane and methanol in a volume ratio of 1:1 as an eluent.
Further, the synthesis method of the pyridinium ion modified trimethylindoline derivative comprises the following steps:
(1) 1-bromohexane modified trimethylindoline derivative
Dissolving and mixing in pyridine, and heating for reaction overnight;
(2) cooling to room temperature, and removing the solvent under reduced pressure to obtain a crude product;
(3) recrystallizing the crude product to obtain the pyridinium ion modified trimethylindoline derivative;
wherein the reaction temperature is 90 ℃;
the recrystallization is to dissolve the crude product by using a small amount of dichloromethane, add the ether according to the volume ratio of the dichloromethane to the ether of 1:100, and stir vigorously.
Further, the synthesis method of the 1-bromohexane modified trimethylindoline derivative comprises the following steps:
(1) 2,3, 3-trimethylindole
Mixing with 1, 6-dibromohexane at a molar ratio of 1:4, dissolving in solvent, N2Carrying out reflux reaction under protection;
(2) cooling to room temperature, and removing the solvent under reduced pressure to obtain a crude product;
(3) purifying the crude product by silica gel column chromatography to obtain the 1-bromohexane modified trimethylindoline derivative;
wherein the solvent is toluene;
the temperature of the reflux reaction is 110 ℃, and the time is 48 hours;
the silica gel column chromatography adopts a mixed solution of dichloromethane and methanol with a volume ratio of 10:1 as an eluent.
Further, the synthesis method of the 2,3, 3-trimethylindole comprises the following steps:
(1) dissolving phenylhydrazine and methyl isopropyl ketone in a solvent according to a molar ratio of 1:1.1, then dripping concentrated sulfuric acid into the solution until the reaction system becomes yellow turbid liquid, and heating and refluxing the solution;
(2) cooling to room temperature, dropwise adding NaOH solution to adjust the solution to be alkaline, extracting with dichloromethane, and removing the solvent under reduced pressure;
(3) purifying by silica gel column chromatography to obtain the 2,3, 3-trimethylindole;
wherein the solvent is absolute ethyl alcohol, the reflux temperature is 80 ℃, and the reflux time is 3 hours;
adding NaOH solution to adjust the pH value to 8;
the silica gel column chromatography adopts a mixed solution of petroleum ether and ethyl acetate with the volume ratio of 3:1 as an eluent.
At the same time, the dicyanovinyl squaraine derivative
The synthesis method comprises the following steps:
(1) malononitrile and diethyl squarate
Dissolving triethylamine and the mixture in a solvent according to a molar ratio of 1:1.1:1.1, and stirring at room temperature for reaction;
(2) after the reaction is finished, placing the reaction bottle in a refrigerator for cooling, then extracting with dichloromethane, and removing the solvent under reduced pressure to obtain the dicyanovinylsquaric acid derivative;
wherein the solvent is benzene, and the stirring reaction time is 6 hours;
the cooling time was 24 hours.
Further, the synthesis method of the diethyl squarate comprises the following steps:
(1) dissolving squaric acid in a solvent, heating and refluxing for reaction, and then removing the solvent by rotary evaporation;
(2) repeating the step (1) for three times, and then carrying out long-time reflux reaction once;
(3) purifying the obtained product by silica gel column chromatography to obtain the diethyl squarate;
wherein the solvent is ethanol, the reflux temperature is 80 ℃, and the time is 3 hours;
the temperature of the long-time reflux is 80 ℃, and the time is 12 hours;
the silica gel column chromatography adopts a mixed solution of petroleum ether and ethyl acetate with the volume ratio of 2:1 as an eluent.
The obtained pyridinium ion modified near-infrared squaric acid dye can be prepared into a fluorescence-responsive diquat probe for fluorescence detection of diquat in the environment.
According to the invention, a pyridinium ion modified 2,3, 3-trimethylindole derivative is connected to a dicyanovinyl squaraine skeleton to obtain a pyridinium ion modified near-infrared squaraine dye. The introduction of the pyridinium ions can enable dye molecules to be completely water-soluble, after the diquat is added, the dye molecules are changed from an aggregation state to a de-aggregation state through electrostatic interaction between the dye molecules and the diquat molecules, and fluorescence is released, so that the rapid detection of the diquat can be realized.
The squarylium dye fluorescent probe obtained by the invention has good water solubility, good stability and excellent optical performance, and can show better specificity and detection sensitivity when being used for the fluorescent detection of diquat in the environment. Through detection, the dye probe has higher specificity to diquat in aqueous solution and other metal ions (Zn)2+、Na+、K+、Mg2+、Ca2+Etc.) and pesticides(paraquat, prosulfocarb, glyphosate, glufosinate, chlormequat chloride and the like) has no response, and the detection limit is 0.49 mu M (3 sigma/k).
Drawings
FIG. 1 is a fluorescence spectrum of diquat (0-100. mu.M) added dropwise to an aqueous solution of pyridinium ion-modified squarylium dye (5. mu.M).
FIG. 2 is a graph showing the linear relationship between the fluorescence intensity of pyridinium ion-modified squarylium dye (5. mu.M) at 685 nm and the diquat concentration (0-10. mu.M) (. lambda.ex=630 nm，slit=10 nm/10 nm，PMT=500 V）。
FIG. 3 is a graph showing the response of pyridinium ion modified squaraine dye (5 μ M) to diquat (100 μ M) in aqueous solutions of different pH values (3-10).
FIG. 4 is a graph showing fluorescence responses before and after dropping diquat (100. mu.M) to the pyridinium ion-modified squaraine dye (5. mu.M) in the time range of 0 to 300 s.
FIG. 5 is a graph showing the fluorescence spectrum response of a pyridinium ion-modified squarylium dye (5 μ M) to different substances of interest in the environment. Wherein 1-K+，2-Na+，3-Cu2+，4-Mg2+，5-Ca2+，6-Mn2+，7-Fe3+，8-CO3 2-，9-SO3 2-，10-HSO3 2-，11-HCO3 -，12-HPO4 -，13-ClO-，14-H2O215-chlormequat chloride, 16-paraquat, 17-glufosinate, 18-glyphosate, 19-mepiquat chloride, 20-maleic hydrazide and 21-diquat.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
20 mL of ethanol is added into a 50 mL round-bottom flask, 2.00 g of squaric acid (17.6 mmol) is added, the reflux reaction is carried out for 3 hours at the temperature of 80 ℃, the ethanol is removed by reduced pressure rotary evaporation after the squaric acid is completely dissolved, the reflux reaction is carried out for 12 hours at the temperature of 80 ℃ after the three times of repeated operation, and after the reaction is finished, silica gel column chromatography separation is carried out by using petroleum ether, ethyl acetate =2:1 (v/v) as an eluent, so that 2.09 g of a light yellow oily liquid product is obtained, and the yield is 70%.1H NMR (400 MHz, CDCl3) δ 4.74 (q,J= 7.1 Hz, 4H), 1.48 (t,J= 7.1 Hz, 6H)。
Example 2
Dicyanovinyl squaraine derivatives
The preparation of (1):
1.77 g of malononitrile (26.8 mmol) was dissolved in 35 mL of dry benzene, placed in a 100 mL round-bottom flask, and 5.00 g of the compound prepared in example 1 was added dropwise
(29.4 mmol), 2.98 g of triethylamine (29.4 mmol) was slowly added to the reaction solution, and the mixture was stirred at room temperature for 6 hours. After the reaction was completed, the reaction flask was placed in a refrigerator to be cooled for 24 hours, extracted with an appropriate amount of dichloromethane, and the organic layer was concentrated in vacuo to obtain 5.28 g of a yellow solid product in 68% yield.1H NMR(400 MHz, CDCl3) δ 9.19 (brs, 1H), 4.76 (q,J= 7.0 Hz, 2H), 3.32-3.25 (m,6H), 1.99 (s, 1H), 1.49 (t,J= 7.1 Hz, 3H), 1.38 (t,J= 7.3 Hz, 9H)。
Example 3
2,3, 3-trimethylindole
Preparation of
20 mL of absolute ethanol containing 500 mg of phenylhydrazine (4.62 mmol) was added to a 50 mL round-bottom flask, 438mg of methyl isopropyl ketone (5.09 mmol) was slowly added dropwise to the solution, the solution became pale yellow, and 0.25 mL of concentrated sulfuric acid was added dropwise within 30 minutes, at which time the reaction system changed againThe reaction solution is yellow turbid liquid and is refluxed for 3 hours at the temperature of 80 ℃. With the increase of the reaction temperature, the color of the reaction system slowly changes from yellow to orange yellow and then to orange-red turbid liquid. After TLC detection till the reaction is completed, the reaction solution is cooled to room temperature, and NaOH solution is added dropwise to adjust the pH value to 8. Extraction was carried out three times with dichloromethane, the solvent was removed under reduced pressure, and purification was carried out by silica gel column chromatography using petroleum ether, ethyl acetate =3:1 (v/v) as an eluent, to obtain 614 mg of a reddish brown oily liquid in a yield of 83%.1H NMR (400 MHz, CDCl3) δ 7.53 (d,J= 7.6 Hz, 1H), 7.35-7.24(m, 2H), 7.18 (t,J= 7.3 Hz, 1H), 2.27 (s, 3H), 1.28 (s, 6H);13C NMR (100MHz, CDCl3): δ 187.84, 153.47, 145.45, 127.41, 124.94, 121.13, 119.69, 53.41,22.91, 15.20。
Example 4
1-bromohexane-modified trimethylindoline derivative
The preparation of (1):
in a 25 mL round-bottom flask, 225 mg (1.41 mmol) of the 2,3, 3-trimethylindole prepared in example 3
And excess 1, 6-dibromohexane (1.38 g, 5.65 mmol) were dissolved in 10 mL of toluene and reacted at 110 ℃ under reflux for 48 hours. After completion of the reaction, purification by column chromatography using a silica gel column using dichloromethane: methanol =10:1 (v/v) as an eluent gave 359 mg of a deep red solid substance with a yield of 64%.1H NMR (400 MHz, CDCl3) δ 7.70(d,J= 3.8 Hz, 1H), 7.60-7.55 (t,J= 7.9 Hz ,2H), 7.51 (d,J= 4.2 Hz, 1H),4.79 (t,J= 7.7 Hz, 2H), 3.42 (t,J= 6.7 Hz, 2H), 3.15 (s, 3H), 2.00-1.95(m, 2H), 1.90-1.85 (m, 2H), 1.65 (s, 6H), 1.60-1.50 (m, 4H);13C NMR (100 MHz,CDCl3) δ 196.26, 141.85, 141.21, 130.39, 129.94, 124.21, 116.63, 54.68,52.32, 34.35, 32.64, 31.27, 29.69, 28.88, 28.19, 26.72, 24.79; HRMS(ESI):Calcd for C17H25BrN+([M]+): 322.1170, Found: 322.1165。
Example 5
Pyridinium ion modified trimethylindoline derivative
The preparation of (1):
180 mg (0.449 mmol) of the 1-bromohexane-modified trimethylindoline derivative prepared in example 4 were added
And 5 mL of pyridine were placed in a 25 mL round-bottom flask and the reaction was stirred at 90 ℃ overnight. After the reaction is finished, reducing pressure to evaporate pyridine, adding a small amount of dichloromethane for dissolution, adding a large amount of diethyl ether according to the volume ratio of the dichloromethane to the diethyl ether of 1:100, and stirring vigorously for half an hour to separate out 130 mg of a purplish black solid product, wherein the yield is 59%.1H NMR (400 MHz, CD3OD) δ9.09 (d,J= 5.6 Hz, 2H), 8.63 (t,J= 7.6 Hz, 1H), 8.15 (t,J= 6.2 Hz, 2H),7.93 (t,J= 2.9 Hz, 1H), 7.80 (t,J= 2.3 Hz ,1H), 7.67 (t,J= 2.4 Hz, 2H),4.72 (t,J= 7.7 Hz, 2H), 4.56 (t,J= 7.5 Hz, 2H), 3.33 (s, 3H), 2.14-2.07(m, 2H), 2.07-1.96 (m, 2H), 1.63 (s, 6H), 1.58-1.53 (m, 4H);13C NMR (100 MHz,CD3OD) δ 196.48, 145.48, 144.62, 141.99, 141.08, 129.78, 129.13, 128.13,123.25, 115.23, 61.43, 54.54, 30.74, 27.30, 25.64, 25.28, 21.45; HRMS (ESI):Calcd for C22H30N2 2+([M]2+/2) 161.1205, Found 161.1200。
Example 6
The near-infrared squarylium dye
The preparation of (1):
the dicyanovinyl squaraine derivative prepared in example 2 was put in a 100 mL three-necked bottle
(39.0 mg, 0.134 mmol) and the pyridinium ion-modified trimethylindoline derivative prepared in example 5
(129 mg, 0.268 mmol) was dissolved in 40 mL of N-butanol-toluene (1: 1, v/v) mixed solvent, connected to a water separator, and N2The reaction was refluxed at 145 ℃ for 5 hours under protection. After the reaction is finished, performing reduced pressure rotary evaporation to remove the solvent, and adopting dichloromethane: purification by silica gel column chromatography with methanol =1:1 (v/v) as eluent gave 85.6 mg of a dark green solid in 69% yield.1HNMR (400 MHz, CD3OD) δ 9.04 (t,J= 10.0 Hz, 4H), 8.61 (t,J= 12.9 Hz, 2H),8.22-8.07 (m, 4H), 7.48 (d,J= 6.2 Hz, 2H), 7.39 (d,J= 6.0 Hz, 2H), 7.34-7.21 (m, 4H), 6.43-6.39 (s, 2H), 4.67 (t,J= 20.6 Hz, 4H), 4.16-4.00 (m,4H), 1.86-1.79 (m, 4H), 1.74 (s, 12H), 1.58 (m, 6H), 1.53-1.45 (m, 6H);13CNMR (100 MHz, CD3OD) δ 172.23, 165.75, 145.46, 144.59, 142.29, 141.66,128.13, 128.00, 124.76, 122.01, 110.47, 88.03, 61.53, 49.40, 46.43, 43.82,38.19, 31.67, 30.75, 29.35, 29.06, 26.68, 25.66, 25.50, 25.43, 22.33; HRMS(ESI): Calcd for C51H56N6O2+([M2+]/2) 384.2258, Found 384.2256。
Application examples
1. A fluorescence titration experiment of diquat was performed in an aqueous solution containing 5. mu.M of the near-infrared squarylium dye obtained in example 6, and the results are shown in FIGS. 1 and 2.
As can be seen from FIG. 1, in the aqueous solution, the fluorescence of the near-infrared squarylium dye solution is in a quenched state, and when diquat is added to the system, the fluorescence intensity at 685 nm is gradually increased, and when diquat is added at a concentration of 100. mu.M, the fluorescence intensity is increased by about 6 times.
As shown in FIG. 2, the concentration of diquat is in the range of 0-10 μ M, and the fluorescence intensity of the solution and the concentration of diquat show good linear relationship (R2=0.985，k=2.46×106). According to the formula 3 sigma/k, the detection limit is calculated to be 4.9×10-7M。
2. The pH in the environment will vary over a range, so fluorescence titration experiments with diquat were performed at different pH (3, 4, 5, 6, 7, 8, 9, 10) and the results are shown in fig. 3.
As can be seen from FIG. 3, at different pH values, the fluorescence of the near-infrared squaraine dye is in a quenched state, and after diquat (100. mu.M) is added, the fluorescence intensity is enhanced by about 6 times, which indicates that the probe has good stability within the pH range of 3-10.
3. The stability of the obtained near-infrared squaraine dye and the response speed of the diquat are examined, and the result is shown in figure 4. As can be seen from the figure, the fluorescence intensity of the squarylium dye itself has no obvious change within 0-300 s, which indicates that the probe has better stability. After the diquat is added, the fluorescence intensity is enhanced by 6 times instantly, which indicates that the probe and the diquat respond instantly.
4. The response of the near infrared squaraine dye to the fluorescence spectrum of some metal ions and other pesticides in the system is observed in figure 5.
As can be seen from FIG. 5, the near-infrared squaraine dye responds significantly only to diquat, but to some metal ions (Zn)2 +、Na+、K+、Mg2+、Ca2+) And other pesticides (chlormequat chloride, paraquat chloride, glufosinate, glyphosate, mepiquat chloride, and captan) have no response, so the probe can be used for quickly detecting the content of the diquat in the environment.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (8)
1. A pyridinium ion modified near infrared squarylium dye characterized by: the structural formula is as follows:
2. a process for the preparation of a near infrared squaraine dye according to claim 1, characterized in that: the method comprises the following steps:
(1) pyridinium ion-modified trimethylindoline derivative
And dicyanovinylsquaric acid derivatives
Mixing, dissolving in solvent, N2Carrying out reflux reaction under protection;
(2) cooling to room temperature, and removing the solvent under reduced pressure to obtain a crude product;
(3) purifying by silica gel column chromatography to obtain the near-infrared squaric acid dye;
wherein the solvent used in the step (1) is a mixed solution of n-butyl alcohol and toluene according to a volume ratio of 1:1, the reflux temperature is 145 ℃, and the reflux time is 5 hours;
and (3) performing silica gel column chromatography by using a mixed solution of dichloromethane and methanol in a volume ratio of 1:1 as an eluent.
3. The method of claim 2, wherein: the synthesis method of the pyridinium ion modified trimethylindoline derivative comprises the following steps:
(1) 1-bromohexane modified trimethylindoline derivative
Dissolving and mixing in pyridine, and heating for reaction overnight;
(2) cooling to room temperature, and removing the solvent under reduced pressure to obtain a crude product;
(3) recrystallizing the crude product to obtain the pyridinium ion modified trimethylindoline derivative;
wherein the temperature of the reaction is 90 ℃;
the recrystallization is to dissolve the crude product by dichloromethane, add the ether according to the volume ratio of the dichloromethane to the ether of 1:100, and stir vigorously.
4. The production method according to claim 3, characterized in that: the synthesis method of the 1-bromohexane modified trimethylindoline derivative comprises the following steps:
(1) 2,3, 3-trimethylindole
Mixing with 1, 6-dibromohexane, dissolving in solvent, N2Carrying out reflux reaction under protection;
(2) cooling to room temperature, and removing the solvent under reduced pressure to obtain a crude product;
(3) purifying the crude product by silica gel column chromatography to obtain the 1-bromohexane modified trimethylindoline derivative;
wherein the solvent is toluene;
the temperature of the reflux reaction is 110 ℃, and the time is 48 hours;
the silica gel column chromatography adopts a mixed solution of dichloromethane and methanol with a volume ratio of 10:1 as an eluent.
5. The method of claim 4, wherein: the synthesis method of the 2,3, 3-trimethylindole comprises the following steps:
(1) dissolving phenylhydrazine and methyl isopropyl ketone in a solvent, then dripping concentrated sulfuric acid into the solvent until a reaction system becomes yellow turbid liquid, and heating and refluxing the yellow turbid liquid;
(2) cooling to room temperature, dropwise adding NaOH solution to adjust the solution to be alkaline, extracting with dichloromethane, and removing the solvent under reduced pressure;
(3) purifying by silica gel column chromatography to obtain the 2,3, 3-trimethylindole;
wherein the solvent is absolute ethyl alcohol, the reflux temperature is 80 ℃, and the reflux time is 3 hours;
adding NaOH solution to adjust the pH value to 8;
the silica gel column chromatography adopts a mixed solution of petroleum ether and ethyl acetate with the volume ratio of 3:1 as an eluent.
6. The method of claim 2, wherein: the dicyanovinyl squaraine derivative
The synthesis method comprises the following steps:
(1) malononitrile and diethyl squarate
Dissolving triethylamine and the mixture in a solvent, and stirring at room temperature for reaction;
(2) after the reaction is finished, placing the reaction bottle in a refrigerator for cooling, then extracting with dichloromethane, and removing the solvent under reduced pressure to obtain the dicyanovinylsquaric acid derivative;
wherein the solvent is benzene, and the reaction time is 6 hours under stirring.
7. The method of claim 6, wherein: the synthesis method of the diethyl squarate comprises the following steps:
(1) dissolving squaric acid in a solvent, heating and refluxing for reaction, and then removing the solvent by rotary evaporation;
(2) repeating the step (1) for three times, and then carrying out long-time reflux reaction once;
(3) purifying the obtained product by silica gel column chromatography to obtain the diethyl squarate;
wherein the solvent is ethanol, the reflux temperature is 80 ℃, and the time is 3 hours;
the temperature of the long-time reflux is 80 ℃, and the time is 12 hours;
the silica gel column chromatography adopts a mixed solution of petroleum ether and ethyl acetate with the volume ratio of 2:1 as an eluent.
8. The use of the pyridinium ion modified near infrared squarylium dye of claim 1 in fluorescent detection of diquat, wherein: the pyridinium ion modified near-infrared squaraine dye is prepared into a fluorescent probe responding to diquat.
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