CN114853656B - Carbazole derivative with AEE characteristic, preparation method and application - Google Patents
Carbazole derivative with AEE characteristic, preparation method and application Download PDFInfo
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- CN114853656B CN114853656B CN202210512491.2A CN202210512491A CN114853656B CN 114853656 B CN114853656 B CN 114853656B CN 202210512491 A CN202210512491 A CN 202210512491A CN 114853656 B CN114853656 B CN 114853656B
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- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- 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
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Abstract
The invention discloses a carbazole derivative with AEE characteristics, which has the following structural formula:
r= -CHO, -OCH in said 1 3 . The compounds were prepared by Suzuki coupling and purified by column chromatography. The carbazole derivative obtained by the invention has excellent AEE effect, the luminous intensity can be improved by 8.2 times and 4 times respectively, the appropriate measuring solvent of the compound is determined by the solvation effect, and the compound DPC-CHO can be used as a fluorescent probe to efficiently and specifically identify tryptophan (the detection limit is 40.8 nM).
Description
Technical Field
The invention relates to an aggregation-induced emission enhancement (AEE) material, in particular to a carbazole derivative with AEE characteristics, a preparation method and application thereof.
Background
Aggregation-induced quenching (ACQ) phenomenon due to pi-pi stacking between molecules has limited the range of applications of conventional fluorescent probes, and in 2001 Tang Benzhong, the concept of aggregation-induced emission (AIE) was first proposed, and intra-molecular motion Restriction (RIM) is generally regarded as the core of the AIE operating mechanism. In 2022, the Park group discovered different phenomena in experiments, and the cyano-substituted trans-diarylethene compound emits light weakly in dilute solution, while the light emission in the aggregation state is enhanced, namely aggregation-induced emission enhancement (AEE), which is widely used in various research fields due to its special light emission phenomenon, especially in the development of OLED materials and photovoltaic materials. Carbazole fragments can be used as electron donating units in luminophores, have been widely used in the design of two-photon excited fluorophores, and most carbazole derivatives can exhibit aggregation-induced emission properties, however, no related report is currently made on the design of organic fluorescent materials with AEE properties by using carbazole groups with AIE properties.
Amino acids are important metabolites present in various natural substrates, tryptophan (Trp), also known as α -aminoindole propionic acid, an essential amino acid involved in various physiological processes, and studies have shown that tumors, infectious diseases and neurological diseases are accompanied by Trp-related metabolic disorders, and tryptophan is an important precursor of melatonin, 5-hydroxytryptamine and nicotinic acid, which are associated with emotional, sleeping and psychological health. Therefore, a simple, high-selectivity and sensitive Trp detection method has important significance in biological research and human health,
the most commonly used method for analyzing amino compounds is reverse phase liquid chromatography-tandem mass spectrometry, and of course, some documents report that the probe detects tryptophan, but most fluorescent probes can only identify a part of 20 natural amino acids instead of one of the 20 natural amino acids, so that it is still a great challenge to distinguish one specific natural amino acid from other amino acids by using a fluorescent detection means.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a carbazole derivative with AEE characteristics, a preparation method and application.
The technical scheme of the invention is as follows: carbazole derivatives with AEE characteristics have the following structural formula:
the R= -CHO, -OCH 3 。
A preparation method of the carbazole derivative with AEE characteristics comprises the following synthetic route:
the method sequentially comprises the following steps of:
will be
4- (9H-carbazol-9-yl) phenylboronic acid, anhydrous potassium carbonate, pd (PPh) 3 ) 4 Placing in a bottle, adding 1, 4-dioxane and distilled water or DMSO and distilled water, stirring under the protection of nitrogen, and heating to completely react; cooling to room temperature after the reaction is finished, extracting with distilled water and dichloromethane, drying with anhydrous sodium sulfate, filtering, and spinning out the solvent; purifying by column chromatography with petroleum ether/ethyl acetate as eluent, and recrystallizing with ethanol to obtain crystal or powder.
The carbazole derivative prepared by the invention has the characteristic of aggregation-induced emission enhancement (AEE), can be used as a fluorescent probe for identifying biological small molecules, has high efficiency and specificity on tryptophan, and has an identification detection limit of 40.8nM.
Drawings
FIG. 1 is a schematic illustration of a compound prepared in accordance with example 1 of the present invention 1 H NMR spectrum.
FIG. 2 shows the preparation of the compound prepared in example 1 of the present invention in THF/C 2 H 5 Fluorescence spectrum and trend of fluorescence in OH mixture.
FIG. 3 is a graph showing fluorescence spectra of the compound of example 1 of the present invention in various solvents.
FIG. 4 is a graph showing fluorescence spectra of the interaction of the compound prepared in example 1 of the present invention with different amino acids as a fluorescent probe.
FIG. 5 is a PL profile of the interaction of the compound prepared in example 1 of the present invention as a fluorescent probe with tryptophan at various concentration gradients.
FIG. 6 is a graph showing the trend of fluorescence intensity of the compound produced in example 1 of the present invention as a fluorescent probe.
FIG. 7 is a graph showing the fluorescence spectrum of a competition experiment of the compound prepared in example 1 of the present invention as a fluorescent probe against amino acid.
FIG. 8 is a diagram of a compound prepared in example 2 of the present invention 1 H NMR spectrum.
FIG. 9 is a THF/C ratio of the compound prepared in example 2 of the present invention 2 H 5 Fluorescence spectrum and trend of fluorescence in OH mixture.
Detailed Description
Example 1:
the preparation method of the carbazole derivative (DCP-CHO) with AEE characteristic is sequentially carried out according to the following steps:
4- (9H-carbazol-9-yl) phenylboronic acid (1.09 g,3.79 mmol), 3, 5-dibromobenzaldehyde (0.5 g,1.89 mmol), anhydrous potassium carbonate (1.75 g,12.7 mmol), pd (PPh) 3 ) 4 (0.1 g,0.087 mmol) was placed in a two-necked flask, which was completely dissolved with a small amount of methylene chloride, then 125mL of DMSO and 25mL of distilled water were added thereto, and the mixture was stirred and heated to 100℃under nitrogen protection to react for 24 hours; cooling to room temperature after the reaction is finished, extracting with 50mL of distilled water and 30mL of dichloromethane, drying with anhydrous sodium sulfate, filtering, and spinning out the solvent; column chromatography purification using petroleum ether/ethyl acetate (100/1.5, v/v) as eluent gave 0.21g of white needle crystals, yield: 18.8%.
The prepared compound 1 The H NMR spectrum is shown in FIG. 1, and the structural formula is as follows:
experiment 1: AEE Performance test of the Compounds prepared in example 1
Although the compounds are highly soluble in most organic solvents, many materials are not soluble in ethanol. In order to examine the AEE activity of the compound prepared in example 1, ethanol was added to its THF solution to prepare THF-C at various concentrations from 0% to 90% by volume 2 H 5 OH solution, record P of mixtureThe L spectrum is shown in FIG. 2 (A). As shown in FIG. 2 (B), the compound DPC-CHO emits stronger fluorescence in pure THF solution, the fluorescence intensity is gradually increased with increasing ethanol content, and the emission intensity reaches the highest when the ethanol content is up to 70%, 8.2 times higher than the original value. The compounds are capable of emitting fluorescence in pure solutions, whereas the fluorescence intensity in mixed solutions is enhanced, which is characteristic of the typical aggregation-induced emission enhancement (AEE) effect.
Experiment 2: solvent Effect of DPC-CHO
The compound DPC-CHO was tested for its emission behavior in different solvents in order to select the appropriate solvent. As shown in fig. 3, the emission behavior of 10 μm compounds in different solvents was different, 10 solvents (N-hexane, toluene, ethyl acetate, tetrahydrofuran, 1, 4-dioxane, acetone, ethanol, N-dimethylformamide, acetonitrile, dimethyl sulfoxide) were selected in this experiment, and generally, DMF solvents were selected in the following test because the polarity of the solvents was increased, the energy difference Δe required for pi→pi×transition was small, the transition probability was increased, the fluorescence wavelength was red shifted, the intensity was also increased, but the dispersion state of the probe in DMF was good, the interaction was stronger, Δe was smaller, and the probe exhibited higher fluorescence intensity in DMF.
Experiment 3: experiments on interactions of DPC-CHO as fluorescent probe with different amino acids
Preparing a concentration of 10 by using DMF as solvent -5 M, the excitation wavelength was 300nm as determined by ultraviolet test, slit width 5:5, adding 100. Mu.M of different amino acids, namely tryptophan (Trp), leucine (Leu), serine (Ser), methylthioamino acid (Met), alanine (Ala), isoleucine (Ile), threonine (Thr), proline (Pro), arginine (Arg), lysine (Lys), aspartic acid (Asp), glutamic acid (Glu), tyrosine (Tyr), phenylalanine (Phe), valine (Val) and cysteine (Cys), histidine (His) and glycine (Gly), and carrying out fluorescence emission spectrometry, wherein a fluorescence spectrum is shown in FIG. 4. The results show that: only when tryptophan was added, the fluorescence intensity was significantly enhanced, whereas no significant fluorescence response was observed when other amino acids were added under the same conditions.
Experiment 4: DCP-CHO as fluorescent probe and Tryptophan interaction experiments with different concentration gradients
The response range of the probe is measured by adding tryptophan (0,10,20, … … and 280 mu M) with different concentration gradients into a probe solution with a certain concentration, as shown in fig. 5, the fluorescence intensity is gradually increased along with the increase of the amino acid concentration, a linear relation graph (shown in fig. 6) of the tryptophan detection of the probe is obtained through linear fitting, the detection limit is calculated to be 40.8nM according to the formula LOD=3σ/k, the detection limit of the nanometer level is lower, and the probe can better realize the trace detection of the tryptophan.
Experiment 5: competitive assay of amino acids with DCP-CHO as fluorescent probe
To determine whether a compound specifically and selectively recognizes tryptophan, fluorescence spectra of leucine (Leu), serine (Ser), methylthioamino acid (Met), alanine (Ala), isoleucine (Ile), threonine (Thr), proline (Pro), arginine (Arg), lysine (Lys), aspartic acid (Asp), glutamic acid (Glu), tyrosine (Tyr), phenylalanine (Phe), valine (Val), cysteine (Cys), histidine (His), glycine (Gly), and tryptophan (Trp) in the presence of the amino acids were studied, respectively, as shown in fig. 7.
The results show that: as shown in FIG. 7, the fluorescence intensity was measured by alternately adding 20. Mu.M of other amino acids and Trp (2 times each) to the probe solution, and it was clearly observed that the effect on the fluorescence intensity was small when the other amino acids were added, and that the intensity was suddenly increased after the addition of the chromophore acid, thereby deducing that the probe not only specifically recognized Trp but also achieved efficient and rapid detection. As is known from the molecular structure of tryptophan, trp is taken as a group with stronger electron donating ability, and is combined with a probe to reduce the power supply ability, so that the photoinduced electron transfer Process (PET) is blocked, and electrons excited in the fluorophore return to the ground state in a radiation transition mode, thereby enhancing fluorescence emission.
Example 2:
the carbazole derivative (DCP-OCH) with AEE characteristics of the invention 3 ) The preparation method of the catalyst comprises the following steps of:
4- (9)H-carbazol-9-yl) phenylboronic acid (1.08 g,3.76 mmol), 3, 5-dibromoanisole (0.5 g,1.88 mmol), anhydrous potassium carbonate (1.75 g,12.7 mmol), pd (PPh) 3 ) 4 (0.1 g,0.087 mmol) was placed in a two-necked flask, 125mL of 1, 4-dioxane and 25mL of distilled water were added thereto, and the mixture was stirred and heated to 90℃under nitrogen protection to react for 24 hours; cooling to room temperature after the reaction is finished, extracting with 50mL of distilled water and 30mL of dichloromethane, drying with anhydrous sodium sulfate, filtering, and spinning out the solvent; column chromatography purification using petroleum ether/ethyl acetate (100/1, v/v) as eluent and recrystallization from methylene chloride and absolute ethanol gave 0.89g of white powder, yield: 80.18%.
The prepared compound 1 The H NMR spectrum is shown in FIG. 8, and the structural formula is as follows:
experiment 1: to investigate whether the compound prepared in example 2 has AEE properties, ethanol solutions were likewise added to the THF solutions of the compounds to prepare THF-C with different volume fractions 2 H 5 The PL spectrum of the OH solution, recorded mixture is shown in fig. 9 (a). As shown in fig. 9 (B), the compound in the original THF solution was able to emit fluorescence, the aggregation degree of the compound was gradually increased as the ethanol content was increased, the fluorescence intensity was also increased, the fluorescence intensity was highest when the ethanol content reached 80%, 4 times higher than the original value, and the fluorescence characteristic also conformed to the aggregation-induced emission enhancement (AEE) characteristic.
Claims (3)
1. A carbazole derivative with AEE characteristics is characterized by having the following structural formula:
2. A process for producing a carbazole derivative having AEE characteristics as claimed in claim 1, characterized by sequentially carrying out the steps of:
will be
4- (9H-carbazol-9-yl) phenylboronic acid, anhydrous potassium carbonate and Pd (PPh) 3 ) 4 Placing in a bottle, adding 1, 4-dioxane and distilled water or DMSO and distilled water, stirring under the protection of nitrogen, and heating to completely react; cooling to room temperature after the reaction is finished, extracting with distilled water and dichloromethane, drying with anhydrous sodium sulfate, filtering, and spinning out the solvent; purifying by column chromatography with petroleum ether/ethyl acetate as eluent, and recrystallizing with ethanol to obtain crystal or powder.
3. The application of carbazole derivative with AEE characteristic as fluorescent probe for identifying small molecular substance is characterized in that: as the application of the identified tryptophan fluorescent probe, the structural formula of the carbazole derivative with AEE characteristics is
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| CN107011244A (en) * | 2017-04-20 | 2017-08-04 | 北京理工大学 | Benzocyclobutane diene with AEE effects and azole derivatives and its preparation |
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| CN107011244A (en) * | 2017-04-20 | 2017-08-04 | 北京理工大学 | Benzocyclobutane diene with AEE effects and azole derivatives and its preparation |
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