CN113980009A - AIE pillar arene fluorescent probe for diamine detection and preparation method and application thereof - Google Patents
AIE pillar arene fluorescent probe for diamine detection and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an AIE pillar aromatic fluorescent probe for diamine detection and a preparation method and application thereof. The pillared aromatic hydrocarbon fluorescent probe molecule is obtained by performing Knoevenagel condensation on functionalized pillared [5] aromatic hydrocarbon and a quinoline-malononitrile structural unit to obtain an intermediate and performing hydrolysis reaction. The invention not only makes good use of the host-guest action between the cavity of the column arene and the guest, but also introduces two anchoring groups at the two ends of the column arene. Through the synergistic effect of a plurality of binding sites and a plurality of acting forces, the AIE column aromatic fluorescent probe can selectively detect 1, 8-octanediamine, 1, 10-decamethylenediamine and diamidododecane from a plurality of alkyl compounds, has the characteristics of simple and convenient operation, high sensitivity and the like in the detection process, and can be used for environmental monitoring, food safety detection and the like.
Description
Technical Field
The invention belongs to the technical field of organic synthesis and analysis detection, and particularly relates to an AIE (air-in-column) arene fluorescent probe for diamine detection, and a preparation method and application thereof.
Background
The alkyl diamine is an important industrial raw material, and particularly, the diamine with a longer alkyl chain (C is more than or equal to 8) has very wide application in the field of fine chemical engineering (for example, 1, 10-diaminodecane is an important intermediate for synthesizing nylon-1010). In recent years, researchers have synthesized a large number of fluorescent sensors that can detect alkyldiamines, but there is also a significant problem in that these fluorescent sensors are not sufficiently selective for diamines having different alkyl chain lengths. (Strutt, N.; Forgan, R.; Spruell, J.; Boros, Y.; Stoddart, J., Mono intersected Pillar [5] arene as a Host for Alkanediamines.J.am. chem. Soc.2011,133, 5668-5671.). This is because all the alkyldiamines belong to the homologous family, their chemical properties are very similar, the main difference being expressed in the number of methylene groups, which makes it difficult to distinguish them from one another. Therefore, the development of a fluorescent probe capable of selectively detecting diamines having a specific alkyl chain length is in urgent need.
The column [5] arene has the characteristics of rigid structure, easy functionalization, good host-guest performance and the like. Currently, one of the most widely studied strategies for the functionalization of column [5] arenes is to covalently attach them to aggregation-induced emission (AIE) groups. A large number of column [5] arenes with AIE properties have been successfully used in the fields of gas adsorption, ion or small molecule detection, dye sensitized solar cells and artificial light collection (Li, J.; Wang, J.; Li, H.; Song, N.; Wang, D.; Tang, B., supra Materials Based on AIE luminescence, Chem. Soc. Rev.2020,49, 1144-. Therefore, the utilization of column [5] arene with AIE property to realize precise identification of the object is a strategy with great application prospect.
The quinoline-malononitrile unit is a good AIE construction framework, and the fluorescence property of the pillared [5] arene can be well improved by introducing the group into the pillared [5] arene. Secondly, two specific anchoring groups are introduced at two ends of the columnar aromatic hydrocarbon, so that the host and the guest can interact with each other in the combination process, and the two anchoring groups can provide two additional interaction forces to improve the combination capability of the host and the guest. Selective detection of a particular diamine can be achieved through multiple binding sites and the synergistic effect of multiple forces.
Disclosure of Invention
The invention aims to design and synthesize an AIE pillar aromatic fluorescent probe for diamine detection aiming at the defects of rare types, poor selectivity and low sensitivity of alkyl diamine fluorescent probes.
The purpose of the invention is realized by the following technical scheme.
The invention provides an AIE pillar aromatic fluorescent probe molecule for diamine detection, which has a structural formula as follows:
the invention provides a method for synthesizing the AIE pillar aromatic fluorescent probe molecule, which comprises the following steps:
(1) taking a compound 1 as an initial raw material, and carrying out a Suzuki coupling reaction with 2-thiopheneboronic acid under the action of a catalyst to generate a compound 2;
(2) the compound 2 and N, N-dimethylformamide are subjected to formylation reaction under the action of a catalyst to generate a compound 3;
(3) the compound 3 and tetraethyl ammonium hydroxide are subjected to hydrolysis reaction to generate a compound 4;
(4) carrying out Williamson reaction on the compound 4 and ethyl bromoacetate to generate a compound 5;
(5) 2-methylquinoline is used as a starting material and carries out substitution reaction with ethyl bromoacetate to generate a compound 6;
(6) reacting the compound 6 with malononitrile to generate a compound 7;
(7) carrying out Knoevenagel condensation reaction on the compound 5 and the compound 7 to generate a compound 8;
(8) the compound 8 is hydrolyzed under the action of strong alkali to generate a target molecule H1;
the reaction formula is as follows:
further, the step (1) comprises the following steps:
placing the compound 1, 2-thiopheneboronic acid and potassium carbonate in a two-neck flask, taking toluene/ethanol/water as a mixed solvent, or taking a tetrahydrofuran/water mixed solvent, and pumping nitrogen for 3 times; adding a proper amount of catalyst in the nitrogen atmosphere, heating to 80-110 ℃, and stirring for reaction for 12-24 hours; after the reaction is finished, cooling to room temperature, adding dichloromethane for extraction, washing an organic layer with water, drying, concentrating, and purifying a crude product through column chromatography, wherein the eluent ratio is petroleum ether/ethyl acetate (10: 1(v/v) to obtain a compound 2; wherein the molar ratio of the compound 1 to the 2-thiopheneboronic acid is 1 (1-2).
Further, the catalyst in the step (1) is Pd (PPh)3)4、Pd(dba)2、PdCl2(dppf)、Pd(PPh3)2Cl2More than one of (1).
Further, the step (2) comprises the following steps:
placing the compound 2 and N, N-dimethylformamide into a two-neck flask, taking dried 1, 2-dichloroethane as a solvent, and pumping nitrogen for 3 times; adding a proper amount of catalyst in the nitrogen atmosphere, then heating to 60-90 ℃, and stirring for reaction for 12-48 hours; after the reaction is finished, cooling to room temperature, adding a potassium carbonate solution, extracting with dichloromethane, washing an organic layer with water, drying, concentrating, and purifying a crude product by column chromatography, wherein the eluent ratio is petroleum ether/ethyl acetate/dichloromethane (25: 4:1 (v/v)) to obtain a compound 3; wherein the molar ratio of the compound 2 to the N, N-dimethylformamide to the catalyst is 1 (1-30) to 1-15.
Further, the catalyst in the step (2) is more than one of phosphorus oxychloride, solid phosgene and thionyl chloride.
Further, the step (3) comprises the following steps:
placing the compound 3 and tetraethyl ammonium hydroxide in a double-neck flask, taking 1, 4-dioxane as a solvent, and pumping nitrogen for 3 times; heating to 50-80 ℃ in a nitrogen atmosphere, stirring for reaction for 0.5-3 hours, and then reacting at room temperature for 1-6 hours; after the reaction is finished, adding dichloromethane for extraction, washing an organic layer with water, drying, concentrating, and separating and purifying a crude product by column chromatography, wherein the eluent ratio is petroleum ether/ethyl acetate (3: 1 (v/v)) to obtain a compound 4; wherein the molar ratio of the compound 3 to the tetraethylammonium hydroxide is 1 (1-4).
Further, the step (4) comprises the following steps:
placing the compound 4, ethyl bromoacetate and potassium carbonate in a two-neck flask, wherein the solvent is one of acetonitrile, toluene, tetrahydrofuran and N, N-dimethylformamide, and extracting nitrogen for 3 times; heating to 60-90 ℃ in a nitrogen atmosphere, stirring and reacting for 8-24 hours; after the reaction is finished, cooling to room temperature, adding dichloromethane for extraction, washing an organic layer with water, drying, concentrating, and purifying a crude product through column chromatography, wherein the eluent ratio is petroleum ether/ethyl acetate (3: 1(v/v) to obtain a compound 5; the molar ratio of the compound 4 to ethyl bromoacetate is 1 (1-5).
Further, the step (5) comprises the following steps:
placing 2-methylquinoline and ethyl bromoacetate in a two-necked flask, and pumping nitrogen for 3 times; heating to 100-120 ℃ in a nitrogen atmosphere, stirring and reacting for 1.5-4 hours; after the reaction is finished, cooling to room temperature, dissolving methanol, and then recrystallizing by using ethyl acetate as a poor solvent, wherein the obtained solid is not further purified to obtain a compound 6; wherein the molar ratio of the 2-methylquinoline to the ethyl bromoacetate is 1 (1-2).
Further, the step (6) comprises the following steps:
placing the compound 6, malononitrile and sodium ethoxide in a double-neck flask, taking ethanol as a solvent, and pumping nitrogen for 3 times; stirring and reacting for 10-24 hours at room temperature under the nitrogen atmosphere; after the reaction is finished, concentrating the reaction solution, adding dichloromethane for extraction, washing an organic layer with water, drying, concentrating, and purifying a crude product by column chromatography, wherein the eluent ratio is petroleum ether/ethyl acetate (1: 1 (v/v)) to obtain a compound 7; the molar ratio of the compound 6 to the malononitrile is 1 (1-4).
Further, the step (7) comprises the steps of:
placing the compound 5, the compound 7 and piperidine in a two-neck flask, taking acetonitrile as a solvent, and pumping nitrogen for 3 times; heating to 70-90 ℃ in a nitrogen atmosphere, stirring and reacting for 8-24 hours; after the reaction is finished, cooling to room temperature, adding methanol until a large amount of solids are separated out, carrying out vacuum filtration to obtain a crude product, and cleaning for 3 times by using methanol to obtain a compound 8; wherein the molar ratio of the compound 5 to the compound 7 is (1-3): 1.
Further, the step (8) comprises the steps of:
placing the compound 8 and a strong base in a two-neck flask, wherein the strong base can be strong base such as NaOH and KOH, and tetrahydrofuran/water is used as a solvent; heating to 60-85 ℃, stirring and reacting for 6-24 hours; after the reaction is finished, cooling to room temperature, concentrating the reaction solution, adding a proper amount of water, dropwise adding a hydrochloric acid solution until no precipitate is generated, carrying out vacuum filtration to obtain a crude product, and carrying out column chromatography separation and purification on the crude product, wherein the eluent ratio is ethyl acetate/methanol 2:1(v/v), so as to obtain a target molecule H1; wherein the molar ratio of the compound to the alkali is 1 (1-20).
The invention also provides application of the AIE pillar aromatic fluorescent probe molecule for diamine detection, and the probe molecule H1 is mixed with diamine and other alkyl chain small molecules in a solvent, and then fluorescence spectrum detection is carried out.
Further, the solvent is ethyl acetate, and the diamine is alkyl diamine.
Further, the alkyl diamine is one or more of 1, 8-octanediamine, 1, 10-decanediamine and diaminododecane.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention reports an AIE pillar aromatic fluorescent probe molecule for diamine detection for the first time, and the preparation method is simple and has the advantages of cheap raw materials, few reaction steps, mild conditions, simple operation, high yield and the like;
(2) the invention not only makes good use of the host-guest action between the cavity of the column arene and the guest, but also introduces two anchoring groups at the two ends of the column arene. Through the synergistic effect of a plurality of binding sites and a plurality of acting forces, the AIE column aromatic hydrocarbon fluorescent probe can selectively detect 1, 8-octanediamine, 1, 10-decamethylenediamine and diaminododecane from a plurality of alkyl compounds such as alkyl diamine, monoamine, alkyl diacid, alkyl diol, dihalide and the like, has simple and convenient operation and high sensitivity in the detection process, and can be used for environmental monitoring, food safety detection and the like.
Drawings
FIG. 1 is a graph showing the relationship between the fluorescence intensity of H1 and the change in the amount of 1, 8-octanediamine added in example 2;
FIG. 2 is a graph showing the relationship between the fluorescence intensity of H1 and the change in the amount of 1, 10-decamethylenediamine added in example 3;
FIG. 3 is a graph showing the relationship between the fluorescence intensity of H1 and the amount of diaminododecane added in example 4;
FIG. 4 is a graph showing the fluorescence change of H1 after addition of other guest in example 5.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
The structural formula of the AIE pillar arene fluorescent probe synthesized in this example is as follows:
the specific synthesis steps are as follows:
(1) synthesis of Compound 2
Placing compound 1(986mg, 1mmol), 2-thiopheneboronic acid (167mg, 1.3mmol) and potassium carbonate (483mg, 3.5mmol) in a two-necked flask, adding a mixed solvent of toluene/ethanol/water (25mL/5mL/2mL), purging nitrogen for 3 times, and adding Pd (PPh)3)4(58mg, 0.05mmol), the reaction was stirred at 90 ℃ for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with dichloromethane, the organic layer was washed with water, dried, concentrated, and the crude product was separated and purified by silica gel column chromatography using petroleum ether/ethyl acetate 10:1(v/v) as an eluent, and dried under vacuum to obtain white solid 2(488mg) with a yield of 53%. Melting point: 183 ℃ and 185 ℃.
1HNMR(500MHz,CDCl3)δ7.32-7.30(m,2H),7.22(s,1H),7.07-7.05(m,1H),6.91-6.90(m,1H),6.78(s,1H),6.76(s,1H),6.76(s,1H),6.74(s,1H),6.73(s,1H),6.68(s,1H),6.67(s,1H),6.03(s,1H),3.95(s,2H),3.85(s,2H),3.82(s,2H),3.81(s,2H),3.74(s,2H),3.72(s,3H),3.67(s,3H),3.66(s,3H),3.63(s,3H),3.62(s,3H),3.56(s,3H),3.53(s,3H),3.49(s,3H).
(2) Synthesis of Compound 3
Compound 2(461mg,0.5mmol) and N, N-dimethylformamide (1mL) were placed in a two-necked flask, 10mL of dried 1, 2-dichloroethane was added, and nitrogen was purged 3 times. Under nitrogen atmosphere, 1mL of phosphorus oxychloride as a catalyst is added under ice-bath conditions, stirred for 40 minutes, and then heated to 85 ℃ to stir for reaction for 48 hours. After the reaction is finished, the reaction product is cooled to room temperature, 10mL of 2mol/L potassium carbonate solution is added under the ice bath condition, then dichloromethane is used for extraction, an organic layer is washed with water, dried and concentrated, and the crude product is separated and purified by silica gel column chromatography with petroleum ether/ethyl acetate/dichloromethane (25: 4: 1) (v/v/v) as an eluent, and is dried in vacuum to obtain 3(360mg) of a white solid with the yield of 76%. Melting point: 144 ℃ and 146 ℃.
1HNMR(500MHz,CDCl3)δ9.87(s,1H),7.64(d,J＝3.8Hz,1H),7.21(s,1H),7.21(s,1H),6.90(d,J＝3.8Hz,1H),6.75(s,1H),6.74(s,1H),6.71(s,1H),6.71(s,1H),6.70(s,1H),6.66(s,1H),6.61(s,1H),5.98(s,1H),3.87(s,2H),3.81(s,2H),3.78(s,2H),3.77(s,2H),3.69(s,5H),3.65(s,3H),3.63(s,3H),3.62(s,3H),3.58(s,3H),3.54(s,3H),3.45(s,3H),3.43(s,3H).
(3) Synthesis of Compound 4
Compound 3(100mg, 0.11mmol) and tetraethylammonium hydroxide (124mg, 0.22mmol) were weighed into a two-necked flask, 3mL of 1, 4-dioxane was added, and nitrogen was purged 3 times. The reaction was stirred for half an hour after warming to 60 ℃ under nitrogen atmosphere, followed by reaction at room temperature for 3 hours. After the reaction was completed, dichloromethane was added for extraction, the organic layer was washed with water, dried, concentrated, and the crude product was separated and purified by silica gel column chromatography using petroleum ether/ethyl acetate ═ 3:1(v/v) as an eluent, and dried under vacuum to give 4(70mg) as a pale yellow solid with a yield of 81%. Melting point: 119 ℃ and 121 ℃.
1HNMR(500MHz,CDCl3)δ9.90(s,1H),7.74(d,J＝3.8Hz,1H),7.40(s,1H),7.13(s,1H),7.11(d,J＝3.8Hz,1H),6.99(s,1H),6.81(s,1H),6.79(s,1H),6.76(s,1H),6.68(s,1H),6.66(s,1H),6.57(s,1H),6.44(s,1H),6.43(s,1H),3.88-3.88(m,5H),3.80(s,2H),3.78(s,2H),3.77(s,4H),3.75(s,3H),3.68(s,3H),3.67(s,3H),3.66(s,3H),3.65(s,3H),3.59(s,3H),3.16(s,3H).
(4) Synthesis of Compound 5
Compound 4(600mg, 0.74mmol), ethyl bromoacetate (247mg, 1.48mmol) and potassium carbonate (413mg, 3mmol) were placed in a two-necked flask, 15mL of acetonitrile was added, and nitrogen was purged 3 times. The temperature is raised to 80 ℃ under the nitrogen atmosphere, and the reaction is stirred for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with dichloromethane, the organic layer was washed with water, dried, concentrated, and the crude product was purified by silica gel column chromatography using petroleum ether/ethyl acetate 3:1(v/v) as an eluent to obtain 5(530mg) as a pale yellow solid, which was dried in vacuo, with a yield of 80%. Melting point: 185 ℃ and 187 ℃.
1HNMR(400MHz,CDCl3)δ9.92(s,1H),7.78(d,J＝3.8Hz,1H),7.34(s,1H),7.11(d,J＝3.8Hz,1H),6.92(s,1H),6.87(s,1H),6.86(s,1H),6.82-6.81(m,3H),6.77(s,1H),6.66(s,1H),6.06(s,1H),4.53(s,2H),3.86(s,2H),3.80-3.78(m,10H),3.73-3.70(m,18H),3.62(s,3H),3.50(s,3H),-1.70(t,J＝7.0Hz,3H).
(5) Synthesis of Compound 6
2-methylquinoline (2.86g, 20mmol) and ethyl bromoacetate (5g, 30mmol) were placed in a two-necked flask and nitrogen was purged 3 times. The temperature was raised to 110 ℃ under nitrogen atmosphere, and the reaction was stirred for 3 hours. After the reaction was completed, it was cooled to room temperature, and after dissolution in methanol, it was recrystallized using ethyl acetate as a poor solvent, and the obtained solid was not further purified to obtain orange-yellow solid 6(5.2g) with a yield of 84%.
(6) Synthesis of Compound 7
Compound 6(6g, 30mmol), malononitrile (4g, 60mmol) and sodium ethoxide (4g, 60mmol) were placed in a two-necked flask, 35mL of ethanol was added, and nitrogen was purged 3 times. The reaction was stirred at room temperature for 16 hours under a nitrogen atmosphere. After the reaction was completed, the reaction solution was concentrated, dichloromethane was added for extraction, the organic layer was washed with water, dried, concentrated, and the crude product was separated and purified by silica gel column chromatography using petroleum ether/ethyl acetate 1:1(v/v) as an eluent, and dried under vacuum to obtain a yellowish green solid 7(1.3g) with a yield of 22%. Melting point: 151 ℃ and 153 ℃.1HNMR(400MHz,CDCl3)δ9.03(d,J＝8.4Hz,1H),7.73-7.69(m,1H),7.44-7.40(m,1H),7.33(d,J＝8.8Hz,1H),6.80(s,1H),4.94(s,2H),4.30(q,J＝7.1Hz,2H),2.52(s,3H),1.30(t,J＝7.1Hz,3H).
(7) Synthesis of Compound 8
Compound 5(300mg, 0.26mmol), compound 7(70mg, 0.24mmol) and 0.3mL of piperidine were placed in a two-necked flask, 7mL of acetonitrile was added, and nitrogen was purged 3 times. The temperature is raised to 80 ℃ under the nitrogen atmosphere, and the reaction is stirred for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, 50mL of methanol was added to precipitate a large amount of solid, and the reaction mixture was filtered under reduced pressure to obtain a crude product, which was then washed with methanol (3X 30mL) to obtain 8(161mg) as a red solid in a yield of 57%. Melting point: 255 ℃ and 257 ℃.1HNMR(400MHz,CDCl3)δ9.14–9.12(m,1H),7.76-7.72(m,1H),7.50-7.46(m,2H),7.33-7.32(m,2H),7.30(d,J＝3.6Hz,1H),7.17(s,1H),6.96(d,J＝3.6Hz,1H),6.92(s,1H),6.89(s,1H),6.87(s,1H),6.82(s,3H),6.76(s,1H),6.69(d,J＝15.4Hz,1H),6.62(s,1H),6.17(s,1H),4.96(s,2H),4.51(s,2H),4.36(q,J＝7.1Hz,2H),3.92(s,2H),3.81-3.78(m,10H),3.73-3.70(m,18H),3.61(s,3H),3.55(s,3H),1.34(t,J＝7.1Hz,3H),-1.67(t,J＝6.7Hz,3H).
(8) Synthesis of H1
Compound 8(190mg, 0.16mmol) and sodium hydroxide (66mg, 1.64mmol) were placed in a two-necked flask, a mixed solvent of tetrahydrofuran/water (25mL/5mL) was added, and the reaction was stirred at 73 ℃ for 12 hours. After the reaction, the reaction solution was cooled to room temperature, 25mL of water was added after the reaction solution was concentrated, a hydrochloric acid solution was further added dropwise until no more precipitate was generated, the crude product was obtained by vacuum filtration, separated and purified by silica gel column chromatography using ethyl acetate/methanol 2:1(v/v) as an eluent, and dried under vacuum to obtain H1(148mg) as a red solid with a yield of 82%. Melting point: 176 ℃ and 178 ℃.
1HNMR(500MHz,CDCl3)δ9.07(d,J＝8.3Hz,1H),7.75-7.72(m,1H),7.52-7.39(m,4H),7.27(s,1H),7.15(s,1H),6.99-6.99(m,1H),6.84(s,1H),6.78(s,1H),6.76(s,1H),6.69-6.59(m,5H),6.55(s,1H),6.15(s,1H),4.95(s,2H),4.43(s,2H),3.93(s,2H),3.84(s,2H),3.77(s,2H),3.76(s,2H),3.74-3.73(m,5H),3.68(s,3H),3.67(s,3H),3.63(s,3H),3.58(s,3H),3.48-3.45(m,9H).
Example 2
H1 was dissolved in ethyl acetate to obtain a probe mother liquor (1X 10)-3mol/L), then 50. mu.l of the mother liquor was taken and diluted to 2mL with ethyl acetate to give 2.5X 10-5mol/L H1 solution. 12 samples were prepared in this manner, and 5X 10 of 0. mu.l (1), 2. mu.l (2), 4. mu.l (3), 6. mu.l (4), 8. mu.l (5), 10. mu.l (6), 12. mu.l (7), 14. mu.l (8), 16. mu.l (9), 18. mu.l (10), 20. mu.l (11), and 24. mu.l (12) were added to each of these samples-3The fluorescence intensity of each sample was measured by mixing 1, 8-octanediamine solution in mol/L, standing for 5 minutes, and the fluorescence intensity was shown in FIG. 1. The measurement result shows that: with increasing addition of 1, 8-octanediamine, the fluorescence emission intensity of the probe molecule H1 is increased. The detection limit of H1 to 1, 8-octanediamine can be calculated to be 16.8 +/-0.1 nM through the results of linear fitting.
Example 3
H1 was dissolved in ethyl acetate to obtain a probe mother liquor (1X 10)-3mol/L), then 50. mu.l of the mother liquor was taken and diluted to 2mL with ethyl acetate to give 2.5X 10-5mol/L H1 solution. 13 samples were prepared in this manner, and 5X 10 microliters (a), 1 microliter (b), 2 microliters (c), 4 microliters (d), 6 microliters (e), 8 microliters (f), 10 microliters (g), 12 microliters (h), 14 microliters (i), 16 microliters (j), 18 microliters (k), 20 microliters (l), and 26 microliters (m) were added to these samples, respectively-3The fluorescence intensity of each of these samples was measured by mixing 1, 10-decamethylenediamine solution in mol/L, standing for 5 minutes, and the like, as shown in FIG. 2. The measurement result shows that: with the increasing addition of 1, 10-decamethylenediamine, the fluorescence emission intensity of the probe molecule H1 is increased. The detection limit of H1 to 1, 10-decamethylenediamine was calculated to be 9.9. + -. 0.1nM from the results of the linear fit.
Example 4
Dissolving H1 inIn ethyl acetate, a probe mother liquor (1X 10) was obtained-3mol/L), then 50. mu.l of the mother liquor was taken and diluted to 2mL with ethyl acetate to give 2.5X 10-5mol/L H1 solution. 14 samples were prepared in this manner, and then 0. mu.l (A), 1. mu.l (B), 2. mu.l (C), 3. mu.l (D), 4. mu.l (E), 6. mu.l (F), 8. mu.l (G), 10. mu.l (H), 12. mu.l (I), 14. mu.l (J), 16. mu.l (K), 18. mu.l (L), 20. mu.l (M), 26. mu.l (N) of 5X 10. mu.l were added to each of these samples-3The fluorescence intensity of each of these samples was measured by mixing a solution of diaminododecane in mol/L, standing for 5 minutes, and the results are shown in FIG. 3. The measurement result shows that: with the increasing addition of diaminododecane, the fluorescence emission intensity of probe molecule H1 is also increasing. The detection limit of H1 to diaminododecane can be calculated to be 7.6 +/-0.2 nM through the results of linear fitting.
Example 5
H1 was dissolved in ethyl acetate to obtain a probe mother liquor (1X 10)-3mol/L), then 50. mu.l of the mother liquor was taken and diluted to 2mL with ethyl acetate to give 2.5X 10-5mol/L H1 solution. In this way, 9 samples were prepared, one of which was used as a blank, and 20. mu.l each of 5X 10 concentration was added to the remaining 8 samples-3The fluorescence intensities of the samples were measured by mixing n-octylamine, ethylenediamine, 1, 4-butanediamine, 1, 6-hexanediamine, octanedionitrile, 1, 8-octanediol, 1, 8-octanedioic acid, and 1, 8-dibromooctane in mol/L, standing for 5 minutes, and then compared with the fluorescence emission curves obtained in example 2, example 3, and example 4, respectively, as shown in FIG. 4. The measurement result shows that: the added guest molecules can not cause the fluorescence emission intensity of the probe molecule H1 to change obviously, so that the fact that the guest molecules and the probe molecule H1 can realize the enhancement of H1 fluorescence by utilizing a plurality of binding sites and the synergistic effect of a plurality of acting forces after the guest molecules are combined with the host and the guest under the condition that the guest simultaneously has two amino groups and an alkyl chain with proper length is proved, and further the selective recognition of 1, 8-octanediamine, 1, 10-decamethylene diamine and diaminododecane is completed.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. An AIE pillar aromatic fluorescent probe molecule for diamine detection is characterized in that the structural formula is as follows:
2. a method for preparing the AIE pillar arene fluorescent probe molecule of claim 1, comprising the steps of:
(1) taking a compound 1 as an initial raw material, and carrying out a Suzuki coupling reaction with 2-thiopheneboronic acid under the action of a catalyst to generate a compound 2;
(2) the compound 2 and N, N-dimethylformamide are subjected to formylation reaction under the action of a catalyst to generate a compound 3;
(3) the compound 3 and tetraethyl ammonium hydroxide are subjected to hydrolysis reaction to generate a compound 4;
(4) carrying out Williamson reaction on the compound 4 and ethyl bromoacetate to generate a compound 5;
(5) 2-methylquinoline is used as a starting material and carries out substitution reaction with ethyl bromoacetate to generate a compound 6;
(6) reacting the compound 6 with malononitrile to generate a compound 7;
(7) carrying out Knoevenagel condensation reaction on the compound 5 and the compound 7 to generate a compound 8;
(8) the compound 8 is hydrolyzed under the action of strong alkali to generate a target molecule H1;
the reaction formula is as follows:
3. the method for preparing the AIE pillar arene fluorescent probe molecule according to claim 2, wherein the molar ratio of the compound 1 to the 2-thiopheneboronic acid in the step (1) is 1 (1-2), the reaction temperature is 80-110 ℃, and the catalyst in the step (1) is Pd (PPh)3)4、Pd(dba)2、PdCl2(dppf)、Pd(PPh3)2Cl2More than one of (1).
4. The method for preparing the AIE pillar aromatic fluorescence probe molecule according to claim 2, wherein the molar ratio of the compound 2 to N, N-dimethylformamide to the catalyst in the step (2) is 1 (1-30) to (1-15), the reaction temperature is 60-90 ℃, and the catalyst in the step (2) is more than one of phosphorus oxychloride, solid phosgene and thionyl chloride.
5. The method for preparing the AIE pillar arene fluorescent probe molecule according to claim 2, wherein the molar ratio of the compound 3 to the tetraethylammonium hydroxide in the step (3) is 1 (1-4), and the reaction temperature is 50-80 ℃.
6. The method for preparing the AIE pillar arene fluorescent probe molecule according to claim 2, wherein the molar ratio of the compound 4 to ethyl bromoacetate in the step (4) is 1 (1-5), and the reaction temperature is 60-90 ℃.
7. The preparation method of the AIE pillar arene fluorescent probe molecule according to claim 2, wherein the molar ratio of the 2-methylquinoline to the ethyl bromoacetate in the step (5) is 1 (1-2), and the reaction temperature is 100-120 ℃; the molar ratio of the compound 6 to the malononitrile in the step (6) is 1 (1-4), and the reaction temperature is room temperature.
8. The method for preparing the AIE pillar arene fluorescent probe molecule according to claim 2, wherein the molar ratio of the compound 5 to the compound 7 in the step (7) is (1-3): 1, and the reaction temperature is 70-90 ℃; the molar ratio of the compound 8 to the alkali in the step (8) is 1 (1-20), and the reaction temperature is 60-85 ℃.
9. The use of AIE pillar arene fluorescent probe molecules for diamine detection as recited in claim 1, wherein probe molecule H1 is mixed with diamine and other alkyl chain small molecules in a solvent and then subjected to fluorescence spectroscopy.
10. The use of AIE pillar arene fluorescent probe molecules for diamine detection according to claim 9, wherein: the solvent is ethyl acetate, and the diamine is alkyl diamine; wherein the alkyl diamine is more than one of 1, 8-octanediamine, 1, 10-decamethylene diamine and diamino dodecane.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130889A (en) * | 2015-09-06 | 2015-12-09 | 西北师范大学 | Quinoline-modified pillararene and preparation thereof and application thereof in performing fluorescence detection on CN<-> in water-containing system |
| CN110183437A (en) * | 2019-05-21 | 2019-08-30 | 华南理工大学 | A kind of double D- π-A type column [5] aromatic hydrocarbons dyestuff and its synthetic method and its application |
| CN113173883A (en) * | 2021-05-11 | 2021-07-27 | 西北师范大学 | 8-hydroxyquinoline functionalized column [5] arene, synthesis thereof and application thereof in detection and adsorption of ethylenediamine |
| CN113185416A (en) * | 2021-04-28 | 2021-07-30 | 南通大学 | Synthesis and application of novel water-soluble pillar aromatic hydrocarbon |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130889A (en) * | 2015-09-06 | 2015-12-09 | 西北师范大学 | Quinoline-modified pillararene and preparation thereof and application thereof in performing fluorescence detection on CN<-> in water-containing system |
| CN110183437A (en) * | 2019-05-21 | 2019-08-30 | 华南理工大学 | A kind of double D- π-A type column [5] aromatic hydrocarbons dyestuff and its synthetic method and its application |
| CN113185416A (en) * | 2021-04-28 | 2021-07-30 | 南通大学 | Synthesis and application of novel water-soluble pillar aromatic hydrocarbon |
| CN113173883A (en) * | 2021-05-11 | 2021-07-27 | 西北师范大学 | 8-hydroxyquinoline functionalized column [5] arene, synthesis thereof and application thereof in detection and adsorption of ethylenediamine |
Non-Patent Citations (4)
| Title |
|---|
| NATHAN L. STRUTT ET AL.: "Monofunctionalized Pillar[5]arene as a Host for Alkanediamines", 《J. AM. CHEM. SOC.》 * |
| NATHAN L. STRUTT ET AL.: "Monofunctionalized Pillar[5]arene as a Host for Alkanediamines", 《J. AM. CHEM. SOC.》, vol. 133, 28 March 2011 (2011-03-28), pages 5668 - 5671 * |
| 刘硕等: "1,4-二甲氧基柱[5] 芳烃的合成及其与1,6-己二胺包结常数的测定", 《化学教育》 * |
| 刘硕等: "1,4-二甲氧基柱[5] 芳烃的合成及其与1,6-己二胺包结常数的测定", 《化学教育》, vol. 38, no. 6, 31 December 2017 (2017-12-31), pages 22 - 25 * |
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