CN113292454B - AIE molecule with cinnamonitrile as framework structure and preparation method and application thereof - Google Patents

AIE molecule with cinnamonitrile as framework structure and preparation method and application thereof Download PDF

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CN113292454B
CN113292454B CN202110621244.1A CN202110621244A CN113292454B CN 113292454 B CN113292454 B CN 113292454B CN 202110621244 A CN202110621244 A CN 202110621244A CN 113292454 B CN113292454 B CN 113292454B
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chiral
cinnamonitrile
compound
aie
aie molecule
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CN113292454A (en
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冯海涛
陈明宇
齐春轩
杨均成
向松
吕盼盼
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Baoji University of Arts and Sciences
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Abstract

The invention designs and develops a series of aggregation-induced emission molecules with cinnamonitrile structures, and can carry out a series of photophysical property modification and application development through functional modification of different groups on the same skeleton structure. Chiral functional groups include chiral amino acids such as alanine, leucine, serine, phenylalanine, and the like; the alkylation functional group comprises an alkyl chain structure such as methane, ethane, propane, butane and the like; the ionizing functional groups include iodate, bromate, hexafluorophosphate, and the like. The molecular platform has a large modification space and application prospect based on a unique structure, and has great potential in the fields of supermolecule assembly, chiral recognition, circularly polarized luminescent materials and the like.

Description

AIE molecule with cinnamonitrile as framework structure and preparation method and application thereof
Technical Field
The invention belongs to the technical field of chiral molecules, relates to a chiral AIE molecule for a fluorescent probe, and in particular relates to an AIE molecule taking cinnamonitrile as a framework structure, and a preparation method and application thereof.
Background
In recent years, although research on chiral compounds (such as amino acids) has been greatly progressed, it is not difficult to find out that efficient, various environmentally-adaptive and biocompatible recognition probes are always lacking for recognition and quantitative analysis of chiral amino acids. Therefore, it is highly desirable to introduce a biological probe with unique aggregation-induced emission (AIE) characteristics, and to make up for the short plate in the research field by means of method innovation and a large number of attempts, and to enrich the application of the aggregation-induced emission material.
Circular Polarized Light (CPL) refers to a phenomenon in which a chiral luminescent material is excited to emit left-handed or right-handed circularly polarized light. The material with circular polarization luminescence property has important application in the aspects of 3D display, optical storage, optical anti-counterfeiting, asymmetric synthesis and the like. In the traditional method for improving the circular polarization luminescence asymmetry of small organic molecules, the self-assembly of molecules is an effective means, but for some molecules with aggregated luminescence quenching property, the method can limit the luminescence efficiency of the material at the same time. In order to solve the problem, luminescent molecules with unique AIE characteristics are introduced in the self-assembly process, so that the problems caused by aggregation luminescence quenching are expected to be solved structurally, and the structural selection and application development of the circularly polarized luminescent material are enriched.
Supramolecular materials have been widely used in a variety of applications including smart materials, drug delivery systems, surfactants, and the like. Chiral supermolecules generated by molecular dynamics or asymmetric stacking of macromolecules have the characteristics of dynamic stimulus response and amplification of chiral signals, and are therefore one of the most promising chiral materials.
Conventional fluorescent dye molecules undergo pi-pi stacking in an aggregated state to cause fluorescence quenching (ACQ), which limits development and application of fluorescent materials to a great extent. In 2001, an aggregation-induced emission (AIE) phenomenon was discovered and reported by the Tang Benzhong institute subject group, and molecules having AIE properties such as tetraphenyl ethylene (TPE) and 9, 10-distyryl anthracene (DSA) have a propeller type molecular structure, and a fluorescence enhancement phenomenon occurs due to limited rotation of benzene rings in an aggregated state. The AIE molecule breaks through the limitation of the aggregation quenching of the traditional fluorescent molecules, injects a new generator into the construction of functional fluorescent materials, especially solid fluorescent materials, and is a very original and advanced progress.
Among the existing AIE molecular research results, TPE has been the most popular and mature research methods and technological paths have been developed, and many applications have been developed. However, the number of documents using cinnamonitrile as a skeleton structure is small, the technical path is not mature, the development in application is less, and more scientific researchers need to put into a great deal of work for research. The present inventors have obtained the present invention by synthesizing and preparing a series of molecules having AIE activity, and detecting and studying their supermolecule assembly behavior by using host-guest effect.
Disclosure of Invention
The invention aims to overcome the defects, find out a high-efficiency mature research method, synthesize AIE molecules with advanced photophysical properties and using cinnamonitrile as a framework structure, develop application scenes with practicability and novelty, and provide a new thought and a new molecular platform for researching novel functional materials.
Based on the above object, the present invention provides an AIE molecule having a cinnamonitrile as a skeleton structure, which has a structure as shown in general formula (a):
in the formula (A), the substituent R1 is selected from one of nitro, amino, o-cresol, 4- (diethylamino) salicylaldehyde, alanine, arginine, leucine, N-carbobenzoxy-leucine, glutamic acid, mandelic acid, chloromandelic acid, serine, phenylalanine, tartaric acid, pyroglutamic acid, cysteine, dibenzoyltartaric acid, di-p-methylbenzotripropionic acid, naproxen (methyl isopropyl acid), valine, tryptophan, proline, methionine, aspartic acid, tyrosine and histidine;
the substituent R2 is selected from hydroxyl, halogen, pyridine or one of the formulas (B), (C) and (D);
in formula (B), the anion X is selected from PF 6 - ，I - ，Br - ，Cl - One of the following; n represents an integer of 0 or more;
the formula (C) is named as N- [ (1R, 2R) -2-aminocyclohexyl ] -2-chloroacetamide, and the formula (D) is named as N- [ (1S, 2S) -2-aminocyclohexyl ] -2-chloroacetamide, which are all chemical structures autonomously synthesized by the inventors.
Further, the halogen is selected from one of F, cl, br, I.
As a preferred embodiment of the present invention, the AIE molecule with cinnamonitrile as a skeleton structure comprises the chemical structures described in the compounds 1-30:
the invention also provides a preparation method of the AIE molecule taking cinnamonitrile as a framework structure, the raw material components for preparing the compounds 1-30 comprise a compound 31 and a compound 32,
specifically, taking the preparation method of the compound 9 as an example, the preparation route is as follows:
those of ordinary skill in the art know that AIE materials find use in almost any luminescent material field, such as smart materials that specifically respond to stimuli (pH, temperature, solvents, pressure, etc.) and reversibly sense, liquid crystal or polarized light materials of tunable refractive index, high efficiency OLED display and illumination materials, optical waveguide materials, selective biochemical sensing materials, trace recognition materials, and cellular organelles, viruses or bacteria in biological systems, vascular imaging materials, etc. The AIE molecule taking the cinnamonitrile as a framework structure provided by the invention is specifically characterized in that according to different fluorescence intensities after the AIE molecule is complexed with arginine with different chiralities, chiral compounds with isomerism such as L-arginine, D-arginine and the like can be visually identified according to the determination of the fluorescence intensities. In addition, the AIE molecules can also be applied to supramolecular assembly and circularly polarized luminescent materials.
Compared with the prior art, the invention has the following beneficial effects or advantages:
the molecular development scheme of the invention starts from a simple molecular structure, synthesizes a precursor compound of the AIE chiral fluorescent probe, synthesizes the designed chiral recognition fluorescent probe through different group modification, and finally separates to obtain a high-purity target product. Cinnamonitrile molecules with AIE properties are less common than traditional chiral molecules, and the invention designs unique molecular structures, which can affect chiral signals and CPL signals through supermolecular assembly effects, which is more rare. Taking chiral recognition as an example, through the experiment of the inventor, in the chiral recognition test, obvious fluorescence difference can be observed through a fluorescence test, and a pair of chiral amino acids can be accurately recognized through complexation, so that the AIE molecule with the cinnamonitrile as a framework structure can be accurately and visually recognized.
Drawings
FIG. 1 is a graph of AIE curve test results for Compound 9.
FIG. 2 is a plot of the fluorescence intensity ratio of Compound 9 at various percentages of poor solvent (THF).
Fig. 3 is a graph showing a change in fluorescence spectrum of 39= [ L-arginine ] = (5.0×10-4M), 40= [ D-arginine ] = (5.0×10-4M) in water to which THF was added.
FIG. 4 shows the application of AIE molecules with unique cinnamonitrile structure in chiral recognition and assembly of circular polarized luminescent material and supermolecule.
FIG. 5 is a simulated configuration of supramolecular assembly of compound 3 with cyclodextrin.
Fig. 6 is a schematic diagram of CD signals in a CPL test.
Detailed Description
The following describes embodiments of the present invention with reference to the drawings and specific embodiments, but the present invention is not limited to the following embodiments.
An AIE molecule having a cinnamonitrile skeleton structure, which has a structure represented by formula (a):
in the formula (A), the substituent R1 is selected from one of nitro, amino, o-cresol, 4- (diethylamino) salicylaldehyde, alanine, arginine, leucine, N-carbobenzoxy-leucine, glutamic acid, mandelic acid, chloromandelic acid, serine, phenylalanine, tartaric acid, pyroglutamic acid, cysteine, dibenzoyltartaric acid, di-p-methylbenzotripropionic acid, naproxen (methyl isopropyl acid), valine, tryptophan, proline, methionine, aspartic acid, tyrosine and histidine;
the substituent R2 is selected from hydroxyl, halogen, pyridine or one of the formulas (B), (C) and (D);
in formula (B), the anion X is selected from PF 6 - ，I - ，Br - ，Cl - One of the following; n represents an integer of 0 or more.
Wherein the halogen is selected from one of F, cl, br, I.
As a preferred embodiment of the present invention, the AIE molecule with cinnamonitrile as a skeleton structure comprises the chemical structures described in the compounds 1-30:
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the invention also provides a preparation method of the AIE molecule taking cinnamonitrile as a framework structure, which comprises the following main raw material compounds,
specifically, taking the preparation method of the compound 9 as an example, the preparation method comprises the following steps:
the raw material components thereof include, in addition to the essential main raw material compounds 31 and 32 described above: p-nitrophenylacetonitrile (CAS: 555-21-5), p-bromobenzaldehyde (CAS: 1122-91-4), pyridine-4-boronic acid (CAS: 1692-15-5), N- (tert-butoxycarbonyl) -D-alanine (CAS: 7764-95-6), triethylamine (CAS: 121-44-8), 1, 4-dioxane (CAS: 123-91-1), anhydrous potassium carbonate (CAS: 584-08-7), tetrakis (triphenylphosphine) palladium (CAS: 14221-01-3), stannous chloride (CAS: 7772-99-8), ethanol (CAS: 64-17-5), hydroxybenzotriazole (CAS: 2592-95-2), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (CAS: 25952-53-8), tetrahydrofuran (CAS: 109-99-9), methyl iodide (CAS: 74-88-4), acetonitrile (CAS: 75-05-8), potassium hexafluorophosphate (CAS: 17084-13-8), methylene chloride (CAS: 64-17-5), and trifluoroacetone (CAS: 76-75-09-75).
Specifically, the preparation steps are as follows:
synthesis of Compound 33: in a 50ml round bottom flask was charged compound 31 (2.28 g,12.33 mmol), compound 32 (2 g,12.33 mmol), 1, 4-dioxane 30ml,3ml triethylamine, and the reaction was stirred at ambient temperature and pressure to give a yellowish green precipitate. The reaction was checked by TLC (ethyl acetate: petroleum ether=1:2 as developing reagent) and stopped after two days. Filtering to obtain yellow-green solid. 3.49g of product are obtained, 4.05g of theoretical yield and 86% of yield.
Synthesis of Compound 34: a250 ml two-necked round bottom flask was charged with compound 33 (2 g,6 mmol), pyridine-4-boronic acid (1.5 g,12 mmol), anhydrous potassium carbonate (4 g,30 mmol) and tetrakis (triphenylphosphine) palladium (0.35 g,0.3 mmol) in an ice bath. Three cycles of evacuating the flask and changing nitrogen were performed, the solvent (96 ml, tetrahydrofuran: water=5:1) was added by syringe, the ice bath was removed, and the reaction was stirred at 80 ℃ under reflux. The reaction was checked by TLC (ethyl acetate: petroleum ether=1:1 as developing reagent) and stopped after 12 hours. After spin-drying, the mixture was dissolved in methylene chloride, extracted three times with water, and dried over anhydrous sodium sulfate. Purifying by column chromatography to obtain yellow green solid. 1.36g of product was obtained in a theoretical yield of 1.96g and a yield of 69%.
Synthesis of Compound 35: a50 ml round bottom flask was charged with compound 34 (1.36 g,4.16 mmol), stannous chloride (3.94 g,20.8 mmol), 22ml ethanol and the reaction was stirred at 95℃under reflux. The reaction was checked by TLC (ethyl acetate: petroleum ether=2:1 as developing reagent) and stopped after 6 hours. The pH was adjusted to 8-9 with sodium bicarbonate (solution changed from red to golden yellow), the solvent was dried with spin-on, dissolved with ethyl acetate, extracted three times with water, the organic phases combined and dried over anhydrous sodium sulfate. Purifying by column chromatography to obtain yellow solid. 1.16g of product was obtained, 1.23g of theoretical yield and 94% of yield.
Synthesis of Compound 36: a50 ml two-necked round bottom flask was charged with 35 (0.71 g,2.3 mmol) of the compound, BOC-D-alanine (1.8 g,9.2 mmol), 1-hydroxybenzotriazole (0.13 g,0.92 mmol) and 1- (3-dimethylaminopropyl) -3-ethyl-carbodiimide hydrochloride (1.31 g,6.9 mmol), and the flask was evacuated and purged with nitrogen three cycles, fresh anhydrous tetrahydrofuran (18 ml) was added by syringe, and the reaction was stirred at 85℃under reflux. The reaction was checked by TLC (ethyl acetate: petroleum ether=1:1 as developing reagent) and stopped after 12 hours. Adjusting pH to 8-9 with sodium bicarbonate, and purifying by column chromatography to obtain yellow solid. 0.875g of product was obtained, 1.07g of theoretical yield and 81% yield.
Synthesis of Compound 37: a50 ml round bottom flask was charged with compound 36 (0.264 g,0.576 mmol), methyl iodide (0.537 ml,8.64 mmol), 15ml acetonitrile and the reaction was stirred at 90℃under reflux. The reaction was checked by TLC (developing solvent dichloromethane: methanol=5:1), after 8 hours, the reaction was stopped and the spin-dried solvent was directly added to the next reaction.
Synthesis of Compound 38: in a flask of the spin-dried compound 37 was added acetone 15ml, potassium hexafluorophosphate (2 ml,14.25 mmol), and the reaction was stirred at 65℃under reflux. TLC detection reaction (developing solvent dichloromethane: methanol=5:1) was performed after 8 hours, and after completion of the reaction, the reaction was stopped and purified by column chromatography to give a yellow solid. 0.254g of product was obtained, 0.278g of theoretical yield and 91.3% yield.
Synthesis of compound 9: a50 ml round bottom flask was charged with compound 38 (0.29 g,0.6 mmol), trifluoroacetic acid (2.5 ml,30 mmol), dichloromethane (10 ml) and the reaction was stirred at ambient temperature and pressure. After 8 hours, the reaction was stopped. The spin-dry solvent is dried by sodium bicarbonate until the pH value is 8-9, and a water-soluble yellow solid is obtained. 0.217g of product was obtained in a theoretical yield of 0.229g and a yield of 94%.
1. The aggregation-induced emission effect fluorescence test of the compound 9 comprises the following specific steps:
(1) Compound 9 prepared according to the present invention was formulated as c 1 ＝1×10 -3 3ml of a mol/L target molecule solution;
(2) Taking c 1 0.5ml of solution, constant volume c 2 ＝1×10 -4 mol/L to 5ml;
(3) Wherein the ratio of the poor solvent is 0%,10%,20%,30%,40%,50%,60%,70%,80%,90%,95%,99%, respectively, and fluorescence test is performed.
2. The chiral recognition fluorescence test of the compound 9 comprises the following specific steps:
(1) Compound 9 prepared according to the present invention was formulated as c 1 ＝1×10 -4 Taking 3mL of a target molecule solution with mol/L, and adding the target molecule solution into a quartz tube;
(2) The L-arginine and the D-arginine are respectively prepared into 5 multiplied by 10 -2 30 mu L of each of the solutions was put into a quartz tube;
(3) To the vial was added 500 μl of poor solvent THF and tested for fluorescence intensity;
(4) Each 500. Mu.L of poor solvent THF was added until the ratio of the poor solvent THF was 99%, and the change in fluorescence intensity and the difference in fluorescence intensity of Compound 9 after complexation with two amino acids were measured.
It can be seen from fig. 1 and 2 that compound 9 belongs to D-a type molecules, and fluorescence quenching in solution is mainly caused by the transition from a Local Excited (LE) state with high luminous efficiency to a tic state with low luminous efficiency; while in the aggregated state, transition from the local excited state to the tic state is prevented, so that the AIE phenomenon occurs.
From FIG. 3, it is clear that L-arginine and D-arginine can be identified based on the difference in fluorescence intensity after complexation of compound 9 with arginine of different chiralities, so that it can be determined that this strategy is feasible for use in the identification of chiral compounds.
As shown in figure 4, the AIE molecule with unique cinnamonitrile structure designed by the invention can be further applied and photophysical property modified on chiral recognition, circular polarization luminescent material and supermolecule assembly strategy, and is a molecular platform with great potential.
In addition, the cinnamonitrile structure compound (exemplified as compound 3) having J aggregation property can be host-guest assembled with a common host compound such as γ -CD (γ -cyclodextrin), and fig. 5 is a simulated configuration of supermolecule assembly of the compound 3 of the present invention with cyclodextrin.
Because the chiral AIE compounds developed in the present invention have chiral groups, a pair of compounds that are chiral to each other should have equal and opposite CPL signals, and fig. 6 is a schematic of CD signals in the CPL test of the compounds of the present invention.
The present invention may be better implemented as described above, and the above examples are merely illustrative of preferred embodiments of the present invention and not intended to limit the scope of the present invention, and various changes and modifications made by those skilled in the art to the technical solution of the present invention should fall within the scope of protection defined by the present invention without departing from the spirit of the design of the present invention.

Claims (4)

1. An AIE molecule taking cinnamonitrile as a framework structure, which is characterized in that the structural formula of the AIE molecule is shown as a compound 9:
。
2. use of the AIE molecule according to claim 1 for visual recognition of chiral compounds, said chiral compounds being L-arginine or D-arginine.
3. Use of the AIE molecule of claim 1 in supramolecular assembly.
4. Use of the AIE molecule of claim 1 in a circularly polarized luminescent material.
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JP2016196447A (en) * 2015-03-11 2016-11-24 国立大学法人九州大学 Fluorescent compound or salt thereof, agent of detecting ionic compound and method of detecting ionic compound
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JP2016196447A (en) * 2015-03-11 2016-11-24 国立大学法人九州大学 Fluorescent compound or salt thereof, agent of detecting ionic compound and method of detecting ionic compound
CN110240699A (en) * 2019-06-14 2019-09-17 湘潭大学 One kind has the side chain liquid crystalline polymer and preparation method thereof of circular polarised luminescence performance

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