CN114853770A - Preparation and application of multifunctional fluorescent probe of five-membered cucurbituril-truxene derivative - Google Patents
Preparation and application of multifunctional fluorescent probe of five-membered cucurbituril-truxene derivative Download PDFInfo
- Publication number
- CN114853770A CN114853770A CN202210369375.XA CN202210369375A CN114853770A CN 114853770 A CN114853770 A CN 114853770A CN 202210369375 A CN202210369375 A CN 202210369375A CN 114853770 A CN114853770 A CN 114853770A
- Authority
- CN
- China
- Prior art keywords
- product
- probe
- reaction
- fluorescent probe
- truxene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
Abstract
The invention discloses a preparation method and application of a multifunctional fluorescent probe of a five-membered cucurbituril-truxene derivative. The probe is characterized in that a truxene derivative is used as a fluorescent group, cucurbituril is used as a recognition group which acts with a target object, the recognition effect of five-membered cucurbituril on metal ions is utilized, the probe can detect various metal ions, the probe has the characteristic of multiple responses, the defect of single detection of a plurality of conventional probes is overcome, the aim of probe multi-functionalization is fulfilled, the detection method of the metal ions established by the probe has the characteristics of wide linear range, low detection limit, good precision and good accuracy, and the detection requirement of trace metal ions in an actual sample can be met.
Description
Technical Field
The invention relates to a fluorescent probe, in particular to a preparation method and application of a multifunctional fluorescent probe of a five-membered cucurbituril-truxene derivative.
Background
Cucurbiturils, also known as cucurbiturils (Ccurbit n urils, Qn s or CB n) s) have the special structural characteristics that 2n bridging methylenes are connected with n glycosidic ureas to form a cavity capable of enclosing different guest molecules and two port macrocyclic compounds which are full of carbonyl oxygen atoms coordinated with metal ions.
The cucurbituril is applied to the aspect of fluorescence detection, and a direct method and a competitive method are adopted at present. The direct method is an analysis method established by limiting the rotation of the object molecules after the object molecules enter the annular cavity of the melon ring so as to enhance the fluorescence of the object molecules, and the detectable substances comprise berberine, palmatine and the like, and the detectable substances in the method have fewer types. Most detection methods also use the principle of competition, namely, a fluorescent probe is assembled by cucurbituril and a proper dye in advance, and a series of compounds are detected in a mode of quenching the fluorescence of the probe due to the competition between a molecule to be detected and the dye molecule. This method has a great limitation in that if the guest molecule does not compete with the dye molecule, it cannot cause fluorescence quenching of the probe, limiting the detection range of application of the method, and such a method cannot detect metal ions.
Aiming at the defects of the cucurbituril in the aspect of fluorescent detection application, the fluorescent group is considered to modify the cucurbituril to enable the cucurbituril to have the fluorescent characteristic, so that the aim of direct detection is fulfilled. The truxene molecule is a fused ring compound with a Y-shaped structure formed by sharing one middle benzene ring by three fluorenes, and has a good rigid plane and a large pi-electron delocalization property. Multiple sites of the truxene, such as C2, C5, C7, C10, C12, C15 and the like, are easily modified, and the truxene derivative with an expanded pi-electron system is obtained by introducing different terminal functional groups, so that the corresponding physical and chemical properties are obtained. The molecule with three linear chains radially extending from the center point of the truxene is in a star-shaped structure. The whole molecule extends towards all directions in space, so that the overlapping of the molecules in the space is avoided, the intermolecular accumulation can be prevented to the maximum extent, and the quenching of fluorescence is effectively inhibited. Therefore, a novel fluorescent probe can be synthesized on the cucurbituril molecule by modifying the fluorescent group of the truxene derivative. In this probe, a truxene derivative serves as a fluorophore, and a cucurbituril serves as a recognition group that interacts with a target. When the probe and the target object are acted, the structure of the probe can be changed to cause the change of the photophysical property. The probe has multiple responses, namely, only substances which can generate host-guest interaction with cucurbituril can cause the change of the probe structure to further influence the fluorescence intensity of the probe. Based on the principle, the invention designs the five-membered cucurbituril-truxene derivative fluorescent probe, and the probe can detect various metal ions by utilizing the recognition effect of the five-membered cucurbituril on the metal ions, has the characteristic of multiple responses, overcomes the defect of single detection of a plurality of conventional probes, and achieves the aim of probe multifunction.
Disclosure of Invention
The invention aims to synthesize a five-membered cucurbituril-truxene derivative fluorescent probe, wherein the five-membered cucurbituril utilizes carbonyl groups of a cavity and a port of the five-membered cucurbituril to identify metal ions, and the truxene derivative is used as a fluorescent group. When the probe and the metal ions are acted, the change of the probe structure can cause the change of the fluorescence intensity and establish a corresponding detection method according to the change. The probe has the characteristics of multifunctional detection and can be used for detecting Cu 2+ ,Pb 2+ ,Fe 3+ ,Fe 2+ , Ag + Five metal ions are detected, and the detection limit can reach 10 -7 -10 -8 mol/L。
The fluorescent probe synthesized by the invention has a multiple-response function, can detect various metal ions, and overcomes the defect that many probes are single in detection at present, namely, one probe can only detect one metal ion. The detection method of the metal ions established by the probe has the characteristics of wide linear range, low detection limit, and good precision and accuracy, and can meet the detection requirements of trace metal ions in actual samples.
The technical scheme of the invention is as follows:
the probe utilizes the recognition effect of five-membered cucurbituril on metal ions, the truxene derivative is used as a fluorescent group, the cucurbituril is used as a recognition group which reacts with the metal ions, and the probe can cause the change of the probe structure after reacting with the metal ions to cause the change of photophysical properties.
The preparation method of the multifunctional fluorescent probe of the five-membered cucurbituril-truxene derivative specifically comprises the following steps:
(1) mixing 120mL of glacial acetic acid and 60mL of concentrated hydrochloric acid to obtain a mixed solution, namely a product A;
(2) accurately weighing a certain amount of 1-indanone, adding the 1-indanone into the mixed solution A, dissolving, placing in a constant-temperature oil bath, slowly heating to 120 ℃, keeping the temperature for refluxing for 24 hours, quickly pouring a reaction product into an ice-water mixed solution while heating after the reaction is finished, quickly stirring while adding, after uniform distribution, adding anhydrous sodium carbonate while stirring, standing after the solution is neutral, completely separating out a yellow product, performing vacuum filtration to obtain a yellow precipitate, repeatedly cleaning with secondary water, then repeatedly cleaning with acetone and dichloromethane until the precipitate is light yellow, and drying in an infrared drying oven to obtain truxene, thus obtaining a B product;
(3) accurately weighing a certain amount of the B product, adding the B product into a 50mL two-neck round-bottom flask, adding anhydrous tetrahydrofuran, placing the two-neck round-bottom flask into an ice water mixed solution under the protection of nitrogen, stirring, taking n-butyl lithium when the temperature in the round-bottom flask reaches 0 ℃, slowly and dropwise adding the n-butyl lithium into the two-neck round-bottom flask, and reacting at 0 ℃ for 2 hours to obtain a C product;
(4) slowly and dropwise injecting 1, 6-dibromohexane into the product C, removing the ice-water mixed solution, continuously stirring at room temperature for reaction for 12 hours, pouring saturated ammonium chloride solution to quench the reaction, repeatedly extracting with a proper amount of dichloromethane for three times, collecting an organic phase, adding a proper amount of anhydrous sodium sulfate into the organic phase, drying, filtering, collecting filtrate, and concentrating the filtrate under reduced pressure to obtain a product D;
(5) separating the product D by using silica gel as a stationary phase and a mixed solvent of petroleum ether and dichloromethane as an eluent, performing component tracing on the eluted eluent by adopting thin-layer chromatography, collecting the eluent only containing 5-bromohexyl truxene, and performing reduced pressure concentration and vacuum drying on the eluent to obtain a target product of the 5-bromohexyl truxene, namely a product E;
(6) accurately weighing a certain amount of monohydroxy substituted quinary cucurbituril ((HO) 1 Q[5]) Adding into a 50mL round-bottom flask with two necks, adding anhydrous N, N-dimethylformamide into the flask, continuously stirring, and slowly injecting anhydrous water into the suspension reaction solutionDimethyl sulfoxide, namely placing a two-neck round-bottom flask into an ice water mixed solution under the protection of nitrogen, adding sodium hydride after the temperature is reduced to 0 ℃, and reacting for 2 hours under stirring to obtain a product F;
(7) and adding a certain amount of the product E into the product F, removing the ice-water mixed solution, continuously stirring at room temperature for reacting for 16h, adding diethyl ether to precipitate the reaction solution after the reaction is finished, standing, filtering, collecting the solid, repeatedly washing the solid with a proper amount of methanol for multiple times, and drying in an infrared drying oven to obtain a brown yellow target product, namely the fluorescent probe.
Specifically, in the preparation method of the fluorescent probe, in the step (2): accurately weighing 20.0g of 1-indanone, adding the 1-indanone into the mixed solution A, dissolving, placing in a constant-temperature oil bath, slowly heating to 120 ℃, keeping the temperature for refluxing for 24 hours, quickly pouring a reaction product into 1L of ice water mixed solution while stirring quickly after the reaction is finished, adding anhydrous sodium carbonate while stirring after the reaction product is uniformly distributed, standing after the solution is neutral, completely separating out a yellow product, performing vacuum filtration to obtain a yellow precipitate, repeatedly cleaning with secondary water, repeatedly cleaning with acetone and dichloromethane until the precipitate is light yellow, and drying in an infrared drying oven to obtain the truxene, thus obtaining the product B.
Specifically, in the preparation method of the fluorescent probe, in the step (3): accurately weighing 0.732g of product B, adding the product B into a 50mL two-neck round-bottom flask, adding anhydrous tetrahydrofuran, placing the two-neck round-bottom flask into an ice-water mixture under the protection of nitrogen, stirring, taking 4.53mL of n-butyl lithium when the temperature in the round-bottom flask reaches 0 ℃, slowly and dropwise adding the n-butyl lithium into the two-neck round-bottom flask, and reacting for 2 hours at 0 ℃ to obtain a product C.
Specifically, in the preparation method of the fluorescent probe, in the step (4): and slowly and dropwise injecting 1.3mL of 1, 6-dibromohexane into the product C, removing the ice-water mixed solution, continuously stirring at room temperature for reaction for 12 hours, pouring saturated ammonium chloride solution to quench the reaction, repeatedly extracting with a proper amount of dichloromethane for three times, collecting an organic phase, adding a proper amount of anhydrous sodium sulfate into the organic phase for drying, filtering, collecting filtrate, and concentrating the filtrate under reduced pressure to obtain a product D.
Specifically, in the preparation method of the fluorescent probe, in the step (5): and (3) separating the D product by using silica gel of 200-300 meshes and using 1 mL/10 mL of eluent as the ratio of petroleum ether to dichloromethane. And (3) tracking the components of the eluted eluent according to thin-layer chromatography, collecting the eluent only containing the 5-bromohexyl truxene, and carrying out reduced pressure concentration and vacuum drying on the eluent to obtain a target product of the 5-bromohexyl truxene, namely a product E.
Specifically, in the preparation method of the fluorescent probe, in the step (6): 80mg of monohydroxy substituted five-membered cucurbituril ((HO) is accurately weighed 1 Q[5]) Adding the mixture into a 50mL two-neck round-bottom flask, adding 2mL anhydrous N, N-dimethylformamide into the flask, continuously stirring, slowly injecting 7mL anhydrous dimethyl sulfoxide into the suspension reaction solution, placing the two-neck round-bottom flask into an ice-water mixed solution under the protection of nitrogen, cooling to 0 ℃, adding 272mg sodium hydride, and reacting for 2 hours under stirring to obtain a product F.
Specifically, in the preparation method of the fluorescent probe, in the step (7): and adding 80mg of the product E into the product F, removing the ice-water mixed solution, continuously stirring at room temperature for reacting for 16h, adding 60mL of diethyl ether to precipitate the reaction solution after the reaction is finished, standing, filtering, collecting the solid, repeatedly washing the solid with a proper amount of methanol for multiple times, and drying in an infrared drying oven to obtain a brown yellow target product, namely the fluorescent probe.
The application of the multifunctional fluorescent probe of the five-membered cucurbituril-truxene derivative is characterized in that the fluorescent probe is placed in an N, N-dimethylformamide-water mixed solvent, and the fluorescent response of the probe to metal ions is measured by a fluorescence spectrometer. Setting the voltage as 600V, the excitation wavelength as 296nm, the excitation slit as 5nm, the emission slit as 5nm, measuring the weakening degree of the fluorescence intensity under the fluorescence emission wavelength of 382nm after the fluorescent probe respectively acts with the metal ions, and respectively establishing the detection method of the corresponding ions according to the weakening of the fluorescence intensity.
In particular to the application, the N, N-dimethylformamide-water mixed solvent comprises the following components in percentage by volume,n, N-dimethylformamide: water-8: the pH of the 2, N, N-dimethylformamide-water mixed solvent is 7, and the metal ion is Cu 2+ ，Pb 2+ ，Fe 2+ ，Fe 3+ ，Ag + 。
Description of the drawings:
FIG. 1 Synthesis route of truxene;
FIG. 25-scheme for the synthesis of bromohexyltrimer indene;
FIG. 3 is a synthetic route of five-membered cucurbituril-truxene derivative;
FIG. 41.0X 10 -5 mol/L of Q [5]Fluorescence spectra of the-Tr probe with different metal ions in DMF/H2O (v/v, 8/2) (metal ions are Cu:. RTM. 2+ ，Pb 2+ ，Fe 2+ ，Fe 3+ ，Ag + ，Sr 2+ ， Mn 2+ ，Hg 2+ ，K + ，Co 2+ ，Na + ，Mg 2+ ，La 3+ ，Zn 2+ ，Ni 2+ ，Li + ，Cr 3+ ，Cd 2+ (ii) a FIG. (a): q5]-Tr，b：Q[5]-Tr+Cu 2+ ，c：Q[5]-Tr+Fe 3+ )。
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Example 1:
1. the preparation method comprises the following steps:
(1) synthesis of truxene: mixing 120mL of glacial acetic acid and 60mL of concentrated hydrochloric acid to obtain a mixed solution, namely a product A; accurately weighing 20.0g of 1-indanone, adding the 1-indanone into the mixed solution A, dissolving, placing in a constant-temperature oil bath, slowly heating to 120 ℃, keeping the temperature for refluxing for 24h, quickly pouring a reaction product into 1L of ice-water mixture while stirring quickly after the reaction is finished, adding anhydrous sodium carbonate while stirring after the reaction product is uniformly distributed, standing after the solution is neutral, completely separating out a yellow product, performing vacuum filtration to obtain a yellow precipitate, repeatedly cleaning with secondary water, repeatedly cleaning with acetone and dichloromethane until the precipitate is light yellow, and drying in an infrared drying oven to obtain the truxene B product.
(2) Synthesis of 5-bromohexyltrimer indene: accurately weighing 0.732g of product B, adding the product B into a 50mL two-neck round-bottom flask, adding anhydrous tetrahydrofuran, placing the two-neck round-bottom flask into an ice-water mixed solution under the protection of nitrogen, stirring, taking 4.53mL of n-butyl lithium when the temperature in the round-bottom flask reaches 0 ℃, slowly and dropwise adding the n-butyl lithium into the two-neck round-bottom flask, and reacting at 0 ℃ for 2 hours to obtain a product C; slowly and dropwise injecting 1.3mL of 1, 6-dibromohexane into the product C, removing the ice-water mixed solution, continuously stirring at room temperature for reaction for 12 hours, pouring saturated ammonium chloride solution to quench the reaction, repeatedly extracting with a proper amount of dichloromethane for three times, collecting an organic phase, adding a proper amount of anhydrous sodium sulfate into the organic phase for drying, filtering, collecting filtrate, and concentrating the filtrate under reduced pressure to obtain a product D; and (3) separating the product D by using 200-300-mesh silica gel as a stationary phase and using a mixed solvent of petroleum ether and dichloromethane of 1ml to 10ml as an eluent, carrying out component tracing on the eluted eluent according to thin-layer chromatography, collecting the eluent only containing 5-bromohexyl truxene, and carrying out reduced pressure concentration and vacuum drying on the eluent to obtain a target product of the 5-bromohexyl truxene, namely the product E.
(3) Five-membered cucurbituril-truxene derivative (Q5)]-Tr) synthesis: 80mg of monohydroxy substituted five-membered cucurbituril ((HO) is accurately weighed 1 Q[5]) Adding the mixture into a 50mL two-neck round-bottom flask, adding 2mL anhydrous N, N-dimethylformamide into the flask, continuously stirring, slowly injecting 7mL anhydrous dimethyl sulfoxide into the suspension reaction solution, placing the two-neck round-bottom flask into an ice water mixed solution under the protection of nitrogen, cooling to 0 ℃, adding 272mg sodium hydride, and reacting for 2 hours under stirring to obtain a product F; and adding 80mg of the product E into the product F, removing the ice-water mixed solution, continuously stirring at room temperature for reacting for 16h, adding 60mL of diethyl ether to precipitate the reaction solution after the reaction is finished, standing, filtering, collecting the solid, repeatedly washing the solid with a proper amount of methanol for multiple times, and drying in an infrared drying oven to obtain a brown yellow target product, namely the fluorescent probe.
The detection method comprises the following steps: accurately weighing Q5 with analytical balance]-Tr fluorescent Probe 1.27mg, dissolved in N, N-Dimethylformamide (DMF) and prepared to a concentration of 1.0X 10 -4 mol/LThe probe solution of (1). Collecting 500mL of Huaxi river water (Guiyang, Guizhou, China), placing the Huaxi river water in a beaker, standing the beaker for 12 hours to remove silt in the river water, filtering the upper river water by using a water-phase filter membrane with the pore size of 0.22 mu m, removing suspended particles in the river water, and adjusting the pH value of the river water to be 7 by using NaOH. Precisely measuring 8mL of probe solution and 2mL of water sample solution in a 10mL centrifuge tube with a plug, uniformly mixing, standing at room temperature for 3min, and measuring by using a fluorescence spectrometer. The voltage was set at 600V, the excitation wavelength was 296nm, the excitation slit was 5nm, the emission slit was 5nm, and the fluorescence intensity of the fluorescent probe at the fluorescence emission wavelength of 382nm was measured.
In order to verify the beneficial effects of the invention, the inventor carries out a great deal of experimental research, and the experimental process and the results are as follows:
first, laboratory glassware and reagent
1. Instrument for measuring the position of a moving object
Cary Eclipse fluorescence spectrometer (Agilent, USA), HX501T electronic balance (Tiandong weighing apparatus factory, Cixi), CSF-1A ultrasonic generator (Shanghai ultrasonic apparatus factory), ultra pure water machine (Chengdouhaokang science and technology, Inc.).
2. Reagent for testing medicine
Ferric chloride, silver nitrate, cupric nitrate trihydrate, lead nitrate were purchased from Beijing Yinaoka technologies, Inc. (analytical grade); n, N-dimethylformamide was purchased from Guangdong Guanghua science and technology, Inc. (analytical purity).
Synthesis of two-and five-membered cucurbituril-truxene derivative fluorescent probe
1. Synthesis of Tripolyindene
The 1-indanone is subjected to aldol condensation and dehydration for many times to form ring to prepare the truxene. Accurately weighing 1-indanone (20.0g, 151mmol), adding the 1-indanone into a mixed solution of glacial acetic acid (120mL) and concentrated hydrochloric acid (60mL) for dissolving, placing the solution into a constant-temperature oil bath kettle after dissolving, slowly heating to 120 ℃, keeping the temperature for refluxing for 24h, pouring a reaction product into 1L of ice-water mixed solution while the solution is hot after the reaction is finished, quickly stirring while pouring, adding anhydrous sodium carbonate after the solution is uniformly distributed to neutralize the unreacted acid, stirring while adding, standing after the solution is neutral, completely separating out a yellow product for about one hour, repeatedly cleaning the obtained yellow precipitate with secondary water after reduced pressure suction filtration, repeatedly cleaning the precipitate with acetone and dichloromethane until the precipitate is light yellow, and drying in an infrared drying box to obtain the truxene. The synthetic route of the trimer indene can be seen in figure 1.
Synthesis of 2, 5-bromohexylidene trimer
Accurately weighing 0.732g (2.4mmol) of truxene, adding the truxene into a 50mL two-neck round-bottom flask, adding 12mL of anhydrous tetrahydrofuran into the round-bottom flask, stirring in an ice water mixture under the protection of nitrogen, taking 4.53mL (7.25mmol 1.6M in hexane) of n-butyl lithium when the temperature in the round-bottom flask reaches 0 ℃, slowly dropwise adding the n-butyl lithium into the two-neck round-bottom flask, reacting at 0 ℃ for 2 hours, slowly dropwise adding 1.3mL of 1, 6-dibromohexane into the reaction liquid, removing the ice water mixed solution, continuously stirring and reacting for 12 hours at room temperature, after the reaction is finished, pouring a saturated ammonium chloride solution into the product to quench the reaction, repeatedly extracting with an appropriate amount of dichloromethane for three times, collecting an organic phase, adding an appropriate amount of anhydrous sodium sulfate into the organic phase, drying, and filtering by using filter paper to remove solids. And (3) separating the solid obtained after the filtrate is subjected to reduced pressure concentration by using silica gel (200-300 meshes) as a stationary phase and using a mixed solvent of petroleum ether and dichloromethane as an eluent (1:10, V/V), tracking the components of the eluted eluent according to thin-layer chromatography, collecting the eluent only containing 5-bromohexyltrimer indene, and performing reduced pressure concentration and vacuum drying on the eluent to obtain the 5-bromohexyltrimer indene. The synthetic route of 5-bromohexyltrimer indene can be seen in FIG. 2.
3. Synthesis of pentabasic cucurbituril-truxene derivative (Q5-Tr)
80mg of monohydroxy-substituted five-membered cucurbituril ((HO)1Q 5) was weighed out accurately and added to a 50mL two-neck round-bottom flask, 2mL of anhydrous N, N-dimethylformamide was added to the flask, and 7mL of anhydrous dimethyl sulfoxide was slowly added to the suspension reaction solution with continuous stirring. Placing the two-neck round-bottom flask into an ice-water mixed solution under the protection of nitrogen, cooling the temperature to 0 ℃, adding 272mg (9.14mol) of sodium hydride into the reaction solution, reacting for 2 hours under stirring, then adding 80mg of 5-bromohexyl truxene into the reaction solution, removing the ice-water mixed solution, and continuously stirring and reacting for 16 hours at room temperature. After the reaction is finished, 60mL of ether is added into the reaction solution to precipitate the reaction solution, the reaction solution is kept stand and filtered, the solid is collected, the solid is repeatedly washed by proper amount of methanol for many times, and the brown yellow target product is obtained after drying in an infrared drying oven. The synthetic route of the five-membered cucurbituril-truxene derivative is shown in figure 3.
III, synthesizing five-membered cucurbituril-truxene derivative fluorescent probe for metal ion Cu 2+ ，Pb 2+ ，Fe 2+ ， Fe 3+ ，Ag + Detection of (2)
1. Detection method
The synthesized quinary cucurbituril-truxene derivative fluorescent probe is respectively mixed with metal ions Cu in a mixed solvent of N, N-Dimethylformamide (DMF) and water (v/v, 8/2, pH 7) 2+ ，Pb 2+ ，Fe 2+ ，Fe 3+ ，Ag + After the action, the fluorescence intensity of the system is reduced to different degrees under the fluorescence emission wavelength of 382nm (the reduction range of the fluorescence intensity is 219-88) (figure 4), so that the detection methods of corresponding ions can be respectively established according to the reduction of the fluorescence intensity.
2. Detection step
In DMF/H 2 Probe Q [5] was investigated in O (v/v, 8/2, pH 7) solution]-Tr and Cu 2+ ，Pb 2+ ，Fe 2+ ， Fe 3+ ，Ag + The linear relationship of (c). First, the concentration range is measured to be 1.0 × 10 -9 mol/L～2.0×10 -5 Fluorescence intensity of 8 probe solutions in mol/L at an emission wavelength of 382 nm. Then adding different metal ions Cu with the same concentration into the probe solution with each concentration respectively 2+ 、Pb 2+ 、Fe 2+ 、Fe 3+ And Ag + After being mixed uniformly, the mixture is placed for 3min at room temperature, and the fluorescence intensity of the system is measured under the emission wavelength of 382 nm. After the probe and the metal ions act, the structure of the probe is changed, so that the fluorescence intensity is changed. Change in fluorescence intensity Δ F ═ F Probe needle —F Probe + metal ion And the concentration of the metal ions is in a linear relation, so that the metal ions can be quantitatively detected. The fluorescence test condition is 600V voltage and 29 excitation wavelength6nm, emission wavelength 382nm, excitation slit 5nm, emission slit 5 nm.
3. The result of the detection
Cu 2+ The linear range of detection is 1.0 × 10 -7 mol/L～1.0×10 -5 Between mol/L, the detection limit is 2.5 multiplied by 10 -8 mol/L；Pb 2+ The linear range of detection is 5.0 × 10 -8 mol/L～8.0×10 -6 Between mol/L, the detection limit is 2.3 multiplied by 10 -8 mol/L；Fe 3+ The linear range of detection is 5.0 × 10 -7 mol/L～2.0×10 -5 Between mol/L, the detection limit is 5.4 multiplied by 10 -8 mol/L。Fe 2+ The linear range of detection is 1.0 × 10 -7 mol/L～1.0×10 -5 Between mol/L, the detection limit is 4.9 multiplied by 10 -8 mol/L; the linear range of Ag + detection is 5.0 × 10 -7 mol/L～ 2.0×10 -5 Between mol/L, the detection limit is 1.2 multiplied by 10 -7 mol/L。
Fourthly, determination of actual water sample
1. Detection step
Accurately weighing Q5 with analytical balance]-Tr fluorescent Probe 1.27mg, dissolved in N, N-Dimethylformamide (DMF) and prepared to a concentration of 1.0X 10 -4 mol/L probe solution. Collecting 500mL of Huaxi river water (Guiyang, Guizhou, China), placing the Huaxi river water in a beaker, standing the beaker for 12 hours to remove silt in the river water, filtering the upper river water by using a water-phase filter membrane with the pore size of 0.22 mu m, removing suspended particles in the river water, and adjusting the pH value of the river water to be 7 by using NaOH. Precisely measuring 8mL of probe solution and 2mL of water sample solution in a 10mL centrifuge tube with a plug, uniformly mixing, standing at room temperature for 3min, and measuring by using a fluorescence spectrometer. Adding 3 water samples with concentration range of 1.0 × 10 -7 mol/L～2.0×10 -5 mol/L of different metal ions Cu 2 + 、 Pb 2+ 、Fe 2+ 、Fe 3+ And Ag + And standing at room temperature for 3min after uniform mixing, measuring the fluorescence intensity of the system at the emission wavelength of 382nm, and substituting into a fitted standard curve to calculate the recovery rate. Setting the voltage at 600V, the excitation wavelength at 296nm, the excitation slit at 5nm, the emission slit at 5nm, and measuring the fluorescence of the fluorescent probe at the fluorescence emission wavelength of 382nmLight intensity.
2. The result of the detection
The synthesized probe is used for detecting river water of Guiyang flower stream, and no Cu is found 2+ ，Pb 2+ ，Fe 2+ ， Fe 3+ And Ag + . Adding Cu with different concentrations into a water sample by adopting a standard addition method 2+ ，Pb 2+ ，Fe 2+ ，Fe 3+ ， Ag + And calculating the recovery rate of the method, and as shown in the table 1, the recovery rate of the metal ions is 76.3-93.8%, and the RSD% is 0.27-1.10%, which shows that the probe detection has good precision and accuracy. Thus, probe Q [5]]-Tr detection of Cu 2+ ，Pb 2+ ，Fe 2+ ，Fe 3+ ，Ag + The method has the advantages of wide linear range, low detection limit and good precision, is a simple and convenient method, and can meet the trace analysis of metal ions in an actual water sample.
TABLE 1 recovery of metal ions in water samples
Fifthly, the invention has the advantages
1. The fluorescent probe synthesized by the invention has a multiple-response function, can detect various metal ions, and overcomes the defect that many probes are single in detection at present, namely, one probe can only detect one metal ion.
2. The detection method of the metal ions established by the probe has the characteristics of wide linear range, low detection limit, and good precision and accuracy, and can meet the detection requirements of trace metal ions in actual samples.
Claims (10)
1. Preparation and application of a five-membered cucurbituril-truxene derivative multifunctional fluorescent probe are characterized in that: the probe utilizes the recognition effect of five-membered cucurbituril on metal ions, the truxene derivative is used as a fluorescent group, the cucurbituril is used as a recognition group which reacts with the metal ions, and the probe can cause the change of the probe structure after reacting with the metal ions to cause the change of photophysical properties.
2. The method for preparing the multifunctional fluorescent probe of the five-membered cucurbituril-truxene derivative according to claim 1, wherein the method comprises the following steps: the preparation method of the probe specifically comprises the following steps:
(1) mixing 120mL of glacial acetic acid and 60mL of concentrated hydrochloric acid to obtain a mixed solution, namely a product A;
(2) accurately weighing a certain amount of 1-indanone, adding the 1-indanone into the mixed solution A, dissolving, placing in a constant-temperature oil bath, slowly heating to 120 ℃, keeping the temperature for refluxing for 24 hours, quickly pouring a reaction product into an ice-water mixed solution while heating after the reaction is finished, quickly stirring while adding, after uniform distribution, adding anhydrous sodium carbonate while stirring, standing after the solution is neutral, completely separating out a yellow product, performing vacuum filtration to obtain a yellow precipitate, repeatedly cleaning with secondary water, then repeatedly cleaning with acetone and dichloromethane until the precipitate is light yellow, and drying in an infrared drying oven to obtain truxene, thus obtaining a B product;
(3) accurately weighing a certain amount of the B product, adding the B product into a 50mL two-neck round-bottom flask, adding anhydrous tetrahydrofuran, placing the two-neck round-bottom flask into an ice water mixed solution under the protection of nitrogen, stirring, taking n-butyl lithium when the temperature in the round-bottom flask reaches 0 ℃, slowly and dropwise adding the n-butyl lithium into the two-neck round-bottom flask, and reacting at 0 ℃ for 2 hours to obtain a C product;
(4) slowly and dropwise injecting 1, 6-dibromohexane into the product C, removing the ice-water mixed solution, continuously stirring at room temperature for reaction for 12 hours, pouring saturated ammonium chloride solution to quench the reaction, repeatedly extracting with a proper amount of dichloromethane for three times, collecting an organic phase, adding a proper amount of anhydrous sodium sulfate into the organic phase, drying, filtering, collecting filtrate, and concentrating the filtrate under reduced pressure to obtain a product D;
(5) separating the product D by using silica gel as a stationary phase and a mixed solvent of petroleum ether and dichloromethane as an eluent, performing component tracing on the eluted eluent by adopting thin-layer chromatography, collecting the eluent only containing 5-bromohexyl truxene, and performing reduced pressure concentration and vacuum drying on the eluent to obtain a target product of the 5-bromohexyl truxene, namely a product E;
(6) accurately weighing a certain amount of monohydroxy substituted quinary cucurbituril ((HO) 1 Q[5]) Adding the mixture into a 50mL two-neck round-bottom flask, adding anhydrous N, N-dimethylformamide into the flask, continuously stirring, slowly injecting anhydrous dimethyl sulfoxide into a suspension reaction solution, placing the two-neck round-bottom flask into an ice water mixed solution under the protection of nitrogen, cooling to 0 ℃, adding sodium hydride, and reacting for 2 hours under stirring to obtain a product F;
(7) and adding a certain amount of the product E into the product F, removing the ice-water mixed solution, continuously stirring at room temperature for reacting for 16h, adding diethyl ether to precipitate the reaction solution after the reaction is finished, standing, filtering, collecting the solid, repeatedly washing the solid with a proper amount of methanol for multiple times, and drying in an infrared drying oven to obtain a brown yellow target product, namely the fluorescent probe.
3. The method for preparing a fluorescent probe according to claim 2, characterized in that: in the step (2): accurately weighing 20.0g of 1-indanone, adding the 1-indanone into the mixed solution A, dissolving, placing in a constant-temperature oil bath, slowly heating to 120 ℃, keeping the temperature for refluxing for 24 hours, quickly pouring a reaction product into 1L of ice water mixed solution while stirring quickly after the reaction is finished, adding anhydrous sodium carbonate while stirring after the reaction product is uniformly distributed, standing after the solution is neutral, completely separating out a yellow product, performing vacuum filtration to obtain a yellow precipitate, repeatedly cleaning with secondary water, repeatedly cleaning with acetone and dichloromethane until the precipitate is light yellow, and drying in an infrared drying oven to obtain the truxene, thus obtaining the product B.
4. The method for preparing a fluorescent probe according to claim 2, characterized in that: in the step (3): accurately weighing 0.732g of product B, adding the product B into a 50mL two-neck round-bottom flask, adding anhydrous tetrahydrofuran, placing the two-neck round-bottom flask into an ice-water mixture under the protection of nitrogen, stirring, taking 4.53mL of n-butyl lithium when the temperature in the round-bottom flask reaches 0 ℃, slowly and dropwise adding the n-butyl lithium into the two-neck round-bottom flask, and reacting for 2 hours at 0 ℃ to obtain a product C.
5. The method for preparing a fluorescent probe according to claim 2, characterized in that: in the step (4): and slowly and dropwise injecting 1.3mL of 1, 6-dibromohexane into the product C, removing the ice-water mixed solution, continuously stirring at room temperature for reaction for 12 hours, pouring saturated ammonium chloride solution to quench the reaction, repeatedly extracting with a proper amount of dichloromethane for three times, collecting an organic phase, adding a proper amount of anhydrous sodium sulfate into the organic phase for drying, filtering, collecting filtrate, and concentrating the filtrate under reduced pressure to obtain a product D.
6. The method for preparing a fluorescent probe according to claim 2, characterized in that: in the step (5): and (3) separating the D product by using silica gel of 200-300 meshes and using 1 mL/10 mL of eluent as the ratio of petroleum ether to dichloromethane. And (3) tracking the components of the eluted eluent according to thin-layer chromatography, collecting the eluent only containing the 5-bromohexyl truxene, and carrying out reduced pressure concentration and vacuum drying on the eluent to obtain a target product of the 5-bromohexyl truxene, namely the E product.
7. The method for preparing a fluorescent probe according to claim 2, characterized in that: in the step (6): 80mg of monohydroxy substituted five-membered cucurbituril ((HO) is accurately weighed 1 Q[5]) Adding the mixture into a 50mL two-neck round-bottom flask, adding 2mL anhydrous N, N-dimethylformamide into the flask, continuously stirring, slowly injecting 7mL anhydrous dimethyl sulfoxide into the suspension reaction solution, placing the two-neck round-bottom flask into an ice water mixed solution under the protection of nitrogen, cooling the temperature to 0 ℃, adding 272mg sodium hydride, and reacting for 2 hours under stirring to obtain a product F.
8. The method for preparing a fluorescent probe according to claim 2, characterized in that: in the step (7): and adding 80mg of the product E into the product F, removing the ice-water mixed solution, continuously stirring at room temperature for reacting for 16h, adding 60mL of diethyl ether to precipitate the reaction solution after the reaction is finished, standing, filtering, collecting the solid, repeatedly washing the solid with a proper amount of methanol for multiple times, and drying in an infrared drying oven to obtain a brown yellow target product, namely the fluorescent probe.
9. The multifunctional fluorescent probe of five-membered cucurbituril-truxene derivative as claimed in claim 1, wherein: the fluorescent probe detection method is characterized in that the fluorescent probe is placed in an N, N-dimethylformamide-water mixed solvent, and the fluorescent response of the probe to metal ions is measured by using a fluorescence spectrometer. Setting the voltage as 600V, the excitation wavelength as 296nm, the excitation slit as 5nm, the emission slit as 5nm, measuring the weakening degree of the fluorescence intensity under the fluorescence emission wavelength of 382nm after the fluorescent probe respectively acts with the metal ions, and respectively establishing the detection method of the corresponding ions according to the weakening of the fluorescence intensity.
10. Use according to claim 9, characterized in that: the N, N-dimethylformamide-water mixed solvent is prepared from the following components in percentage by volume: water-8: the pH of the 2, N, N-dimethylformamide-water mixed solvent is 7, and the metal ion is Cu 2+ ，Pb 2+ ，Fe 2+ ，Fe 3+ ，Ag + 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210369375.XA CN114853770A (en) | 2022-04-08 | 2022-04-08 | Preparation and application of multifunctional fluorescent probe of five-membered cucurbituril-truxene derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210369375.XA CN114853770A (en) | 2022-04-08 | 2022-04-08 | Preparation and application of multifunctional fluorescent probe of five-membered cucurbituril-truxene derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114853770A true CN114853770A (en) | 2022-08-05 |
Family
ID=82628937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210369375.XA Pending CN114853770A (en) | 2022-04-08 | 2022-04-08 | Preparation and application of multifunctional fluorescent probe of five-membered cucurbituril-truxene derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114853770A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115626930A (en) * | 2022-10-20 | 2023-01-20 | 贵州大学 | Synthetic method and application of seven-element cucurbituril-truxene derivative |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030212268A1 (en) * | 2001-07-04 | 2003-11-13 | Kimoon Kim | Water-and organic-soluble cucurbituril derivatives, their preparation methods, their separation methods and uses |
| US20060292570A1 (en) * | 2003-09-04 | 2006-12-28 | Technion Research & Development Foundation Ltd. | Novel synthetic binding pairs and uses thereof |
| CN107502339A (en) * | 2017-07-19 | 2017-12-22 | 贵州大学 | A kind of ratio fluorescent probe for identifying nilotinib and its preparation and recognition methods |
-
2022
- 2022-04-08 CN CN202210369375.XA patent/CN114853770A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030212268A1 (en) * | 2001-07-04 | 2003-11-13 | Kimoon Kim | Water-and organic-soluble cucurbituril derivatives, their preparation methods, their separation methods and uses |
| US20060292570A1 (en) * | 2003-09-04 | 2006-12-28 | Technion Research & Development Foundation Ltd. | Novel synthetic binding pairs and uses thereof |
| CN107502339A (en) * | 2017-07-19 | 2017-12-22 | 贵州大学 | A kind of ratio fluorescent probe for identifying nilotinib and its preparation and recognition methods |
Non-Patent Citations (2)
| Title |
|---|
| 支青主编: "《有机化学实验 第2版》", vol. 1, 贵州大学出版社 , pages: 61 * |
| 王莎莎: "基于五元瓜环衍生物新型荧光探针的构筑", pages 30 - 32 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115626930A (en) * | 2022-10-20 | 2023-01-20 | 贵州大学 | Synthetic method and application of seven-element cucurbituril-truxene derivative |
| CN115626930B (en) * | 2022-10-20 | 2024-04-09 | 贵州大学 | Synthesis method and application of seven-membered cucurbituril-trimeric indene derivative |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liang et al. | A highly selective colorimetric chemosensor for detecting the respective amounts of iron (II) and iron (III) ions in water | |
| CN106632064B (en) | Reversible dihydroxy phenanthroimidazole Hg2+Fluorescent probe synthesis and methods of use | |
| CN104910316B (en) | A kind of macromolecule colorimetric nano film material and preparation method thereof and it is used for Fe3+With the application of pyrophosphate context of detection | |
| CN107382905B (en) | Probe for detecting multiple ions and application thereof | |
| CN108358882B (en) | Rhodamine-like compound and synthesis method and application thereof | |
| Hu et al. | Synthesis, structural characterization, and fluorescent chemosensory properties of novel molecular clips based on diethoxycarbonyl glycoluril | |
| CN114853770A (en) | Preparation and application of multifunctional fluorescent probe of five-membered cucurbituril-truxene derivative | |
| Li et al. | Synthesis and properties of a novel FRET-based ratiometric fluorescent sensor for Cu 2+ | |
| CN111393461B (en) | Palladium ion fluorescent probe compound based on BODIPY and synthetic method thereof | |
| CN111138431B (en) | Reactive fluorescent probe for detecting thiophenol and synthetic method and application thereof | |
| CN108997401B (en) | Fluorescent probe for detecting lead ions and preparation method thereof | |
| CN109232594B (en) | Spiropyran-bipyridine derivative and naked eye detection of copper (II) by spiropyran-bipyridine derivative | |
| Chang et al. | ICP-OES determination of trace metal ions after preconcentration by 4-(8-hydroxy-5-quinolylazo) naphthalenesulfonic acid modified silica gel | |
| CN107831165B (en) | Double-channel copper ion detection test paper and preparation method thereof | |
| Xu et al. | Highly selective and sensitive optical probe for Fe 3+ based on a water-soluble squarylium dye | |
| CN115304750A (en) | Covalent organic framework material, ligand, fluorescent sensor and application thereof | |
| CN112679459A (en) | Near-infrared hydrazine fluorescence sensor and preparation method and application thereof | |
| CN113588380A (en) | Method for measuring chelating rate of sugar alcohol chelated potassium by combining organic solvent precipitation method and conductivity method | |
| CN113307763A (en) | Amino acid derivative, preparation method thereof and application of amino acid derivative as acid-base indicator and fluorescent probe | |
| Li et al. | NIR squaraine dyes for dual colorimetric and fluorescent determination of Fe 3+, Cu 2+, and Hg 2+ ions | |
| CN111413308A (en) | Application of rare earth element complex in detection of trace nitrite in mineral water | |
| CN106256857B (en) | It is a kind of applied to the ethyl violet B of offset plate material and its HPLC assay methods of content | |
| CN105505376B (en) | A kind of Hg containing double carbon-sulfur bond structure rhodamines2+Fluorescence probe and preparation method and application | |
| CN114478364B (en) | For detecting Fe 3+ Fluorescent probe and preparation method and application thereof | |
| CN113801131B (en) | Fluorescent probe with high sensitivity and high selectivity and ferric ion recognition and detection thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |