A,A'-dihydroxynaphthoylhydrazone-functionalized conjugated column[5] aromatic hydrocarbon and its synthesis and application

Abstract

The application provides an A,A'-dihydroxynaphthaldehyde hydrazone functionalized conjugated pillar[5]arene and a synthesis method thereof. First, a di-m-benzoic acid methyl ester functionalized conjugated pillar[5]arene and hydrazine hydrate are used as substrates to react in anhydrous ethanol solvent to obtain a di-m-benzoic acid hydrazine functionalized conjugated pillar[5]arene; then the di-m-benzoic acid hydrazine functionalized conjugated pillar[5]arene and 2-hydroxy-1-naphthaldehyde are used as substrates to react in anhydrous methanol to obtain the A,A'-dihydroxynaphthaldehyde hydrazone functionalized conjugated pillar[5]arene HGP5. The sensor molecule HGP5 in the application can detect Arg in a "colorimetric fluorescence" dual-channel mode, and can also detect Al 3+ in a super-sensitive mode under fluorescence. In addition, the chemical sensor has potential application in cell imaging, and can detect Al 3+ and Arg in cells. The application provides a new idea for developing a novel supramolecular fluorescent material for detecting Arg and Al 3+ in an aqueous solution.

Description

Technical Field

[0001] This invention relates to an A,A'-dihydroxynaphthoylhydrazone-functionalized conjugated column[5] aromatic HGP5 chemical sensor. This invention also relates to the synthesis of the HGP5 chemical sensor and its application in the detection of Arg and Al in solution. 3+ Its applications fall under the fields of chemical synthesis and molecular detection. Background Technology

[0002] Arginine is one of the essential amino acids for the human body. The most common form is L-arginine (Levo-arginine), which can be found in many health supplements. It is used in biochemical research to lower blood ammonia levels, treat hepatic coma, and is an important component of amino acid infusions and comprehensive amino acid preparations. Arginine also serves as a nutritional supplement, providing energy for immune cells, helping to maintain immune function, activate immune cells, synthesize collagen needed for damaged tissues, and assist in wound healing. Arginine plays a significant role in biological, biochemical, and metabolic processes in both human and animal experiments, including the formation of polyamines, creatinine, urea nitrogen, and nitric oxide, as well as the synthesis of arginine and pyrimidines. Besides participating in the formation of cell and tissue proteins, arginine also influences hormone release and nucleic acid formation.

[0003] Furthermore, as the most abundant metallic element and the third most abundant element in the Earth's crust, aluminum is widely used in various applications. Nevertheless, excessive Al in the body... 3+ It can lead to various health problems, including Alzheimer's disease (AD) and Parkinson's disease. The World Health Organization has classified Alzheimer's disease as a serious health concern. 3+ Listed as a source of food contamination, and Al in drinking water 3+ The maximum concentration was set at 7.41 mM. Furthermore, acid rain-induced water-soluble Al... 3+ It is highly toxic to the growing plants and the environment. Therefore, efficient identification of Arg and Al is crucial. 3+ This is extremely important. The tightening of environmental standards necessitates the detection of samples with low or even ultra-low concentrations, requiring such smart materials to possess ultra-sensitive response capabilities to the target substance (ultra-sensitive response refers to a detection limit (LOD) of 10 for the sample). -9 M) Therefore, in order to improve the identification of Arg and Al 3+To enhance selectivity and sensitivity, this invention introduces a large conjugated system into the design of a columnar aromatic chemical sensor to improve its signal response capability to host-guest interactions. Simultaneously, acylhydrazones are introduced to functionalize the conjugated columnar aromatic hydrocarbon, utilizing the synergistic effect between acylhydrazones and columnar aromatic hydrocarbons to improve the selective binding capability to the target guest. This type of columnar aromatic hydrocarbon can firstly improve the selectivity and sensitivity to the guest by utilizing the synergistic effect between the cavity and the acylhydrazone group; secondly, due to its large conjugated structure, it can effectively enhance intramolecular charge transfer, thereby improving its optical response signal. Therefore, this invention discloses the synthesis of an A,A'-dihydroxynaphthoylhydrazone-functionalized conjugated columnar aromatic hydrocarbon HGP5 and its effect on Arg and Al... 3+ Highly sensitive detection. HGP5 for Al 3+ The limit of detection for fluorescence is 7.94 × 10⁻⁶. -9 M has reached the level of ultra-sensitive detection. Summary of the Invention

[0004] The purpose of this invention is to provide an A, A'-dihydroxynaphthoylhydrazone-functionalized conjugated column[5] aromatic HGP5 chemical sensor; Another objective of this invention is to provide a method for synthesizing the above-mentioned A, A'-dihydroxynaphthoylhydrazone-functionalized conjugated column[5] aromatic chemical sensor HGP5; Another objective of this invention is to provide the A,A'-dihydroxynaphthoylhydrazone-functionalized conjugated column[5] aromatic chemical sensor HGP5 for detecting Arg and Al 3+ Applications in [the field].

[0005] I. A, A'-Dihydroxynaphthoylhydrazone-functionalized conjugated column[5] aromatic hydrocarbon HGP5 and its synthesis The molecular formula of A,A'-dihydroxynaphthoylhydrazone-functionalized conjugated column[5] aromatic hydrocarbon HGP5 is C 87 H 86 N4O 12 The structural formula is: The crystal structure is as follows: .

[0006] The preparation method of the A, A'-dihydroxynaphthoylhydrazone-functionalized conjugated column[5] aromatic chemical sensor HGP5 of the present invention includes the following steps: (1) Synthesis of conjugated column[5] aromatic 1 functionalized with methyl di-m-benzoate: using OTf-EtP[5] [1]Using trimethoxycarbonylphenylboronic acid as a substrate, and THF / H2O mixture as a solvent, Na2CO3 and Pd(PPh3)4 were added and reacted at 75~85℃ for 30~40h under nitrogen protection. After the reaction was completed, water was added and extracted with ethyl acetate. The combined organic phases were concentrated and the residue was subjected to column chromatography to obtain a white solid, which is the methyl di-m-benzoate functionalized conjugated column[5] aromatic 1.

[0007] The molar ratio of OTf-EtP[5] to trimethoxycarbonylphenylboronic acid is 1:5; the volume ratio of THF to H2O in the THF / H2O mixture is 5:1. The structural formula of OTf-EtP[5] is: ;OTf-EtP[5] Preparation Reference T. Ogoshi, D. Yamafuji, T. Akutsu, M. Naito, TAYamagishi. Achiral guest-induced chiroptical changes of a planar-chiral pillar[5]arene containing one pi-conjugated unit[J]. Chem. Comm., 2013, 49, 8782-4. (2) Synthesis of bis-benzoylhydrazine-functionalized conjugated[5]arene 2: Using hydrazine hydrate and methyl bis-benzoate-functionalized conjugated[5]arene as substrates and anhydrous ethanol as solvent, the reaction was carried out at 75~85℃ for 20~25h. After the reaction was completed, a white solid was precipitated. The solid was filtered and washed with hot ethanol. The product obtained was bis-benzoylhydrazine-functionalized conjugated[5]arene 2. The molar ratio of methyl bis-benzoate-functionalized conjugated[5]arene 1 to hydrazine hydrate was 1:2~1:3.

[0008] (3) Synthesis of A, A'-dihydroxynaphthylhydrazone-functionalized conjugated aromatic [5]: Using bis-m-benzoylhydrazine-functionalized conjugated aromatic [5] 2 and 2-hydroxynaphthaldehyde as substrates and anhydrous methanol as solvent, the reaction was carried out at 60~80℃ for 20~24h. After the reaction was completed, a green solid was precipitated. The solid was filtered and washed with ethanol. The product obtained was A, A'-dihydroxynaphthylhydrazone-functionalized conjugated aromatic [5] HGP5. The molar ratio of bis-m-benzoylhydrazine-functionalized conjugated aromatic [5] 2 and 2-hydroxynaphthaldehyde was 1:2~1:3.

[0009] The molecular formula of the chemical sensor prepared above is: C 87 H 86 N4O 12 The synthetic route for HGP5 is as follows: The proton and carbon spectra of intermediate 1 are shown in [reference needed]. Figure 1 and Figure 2 The mass spectrum, proton spectrum, and carbon spectrum of intermediate 2 are shown in [reference needed]. Figure 3 , Figure 4 and Figure 5 The mass spectra, proton and carbon spectra of the sensor molecule HGP5 are shown in [reference needed]. Figure 6 , Figure 7 and Figure 8 .

[0010] II. Application of the HGP5 chemical sensor for Arg detection 1. UV and fluorescence properties of the chemical sensor HGP5 Studies on the fluorescence properties of the HGP5 sensor show that it exhibits good solubility in a DMSO / H2O (v:v=9:1) solution. When the excitation wavelength is 370 nm, the HGP5 sensor molecule shows no fluorescence emission, exhibiting very low fluorescence intensity, and no new peaks appear in the ultraviolet light.

[0011] 2. The dual-channel colorimetric fluorescence sensor identifies arginine. In a solution of the colorimetric fluorescence sensor HGP5 in a DMSO / H2O (v:v=9:1) system (C HGP5 =2×10 -5 Arg, Gly, Phe, Asn, Thr, Met, Ile, Leu, Ser, His, Trp, Ala, Gln, Glu, Asp, Pro, Lys, Val, and Cys were added to M, and the changes in fluorescence and color of the solution were observed. Figure 9 The fluorescence spectra (λ) of different amino acids were obtained by adding different amino acids to the solution of the sensor molecule HGP5 in the DMSO:H2O (v:v=9:1) system of this invention. ex =370 nm). The results showed that only the addition of Arg activated the fluorescence of the HGP5 sensor in the DMSO:H2O (v:v=9:1) system. The addition of other amino acids did not activate the fluorescence of the HGP5 sensor in the DMSO:H2O (v:v=9:1) system. Furthermore, we found that HGP5 could also detect Arg "without the naked eye" in DMSO:H2O (v:v=9:1). After adding different amino acids, only Arg changed the solution color to orange-yellow; other ions had no effect, and a change in intensity was also observed in the ultraviolet light. Figure 10 This indicates that HGP5 can detect Arg using a dual-channel UV fluorescence method in DMSO: H2O (v: v=9: 1).

[0012] Fluorescent titration experiments showed that the limit of detection for Arg by the HGP5 sensor was 3 × 10⁻⁶. -8 M (as) Figure 11 , 12 (As shown).

[0013] UV titration experiments showed that the limit of detection for Arg by the HGP5 sensor is 2.99 × 10⁻⁶. -8 M (as) Figure 13 , 14 (As shown).

[0014] 3. Assembly performance study of Arg and HGP5 To investigate the assembly properties of compounds Arg and HGP5, we used... 1 H NMR was used to study its assembly mechanism, such as Figure 15 As shown, in 1 In the 1H NMR titration spectrum, when Arg is added, the H on HGP5... a and H b The disappearance of the monomer indicates that the protons on the bisphenol and imide groups of HGP5 have been deprotonated, since Arg is a basic amino acid. Simultaneously, the HGP5 signal... c H d The high-field shift is evident, with H1 and H2 at Arg showing a shift towards the higher field. This indicates that the guanidinium group of Arg, after gaining a proton, enters the cavity of HGP5 through CH∙∙∙O bonds and cation-π interactions, revealing the mechanism of the interaction between Arg and HGP5 (see [mechanism details]). Figure 16 The morphological structure before and after assembly was evaluated using scanning electron microscopy. Figure 17 It was observed that HGP5 had a regular spherical morphology, while after assembly, the morphology became a layered cross-linked network, indicating that Arg and HGP5 were successfully assembled.

[0015] 4. HGP5 conjugated system supramolecular sensor test paper The study investigated the effects of adding different concentrations (1×10⁻⁶). -8 M ~ 1×10 -1 After M) Arg, the fluorescence and colorimetric changes of the HGP5-based test strip ( Figure 18 ).

[0016] 5. Research on quantitative detection of Arg based on supramolecular sensor of HGP5 conjugated system Take 2 mL (2×10) -5 Add HGP5 standard solution (M) to a fluorescent cuvette, add Arg standard solution of different concentrations (1~35 mmol / L), measure the fluorescence spectrum of the mixture, and establish a standard curve based on the relationship between fluorescence intensity and arginine concentration. Figure 19 When the Arg concentration is between 1 and 35 mmol / L, quantitative detection of Arg can be achieved.

[0017] 6. Research on Arg detection in living cells based on HGP5 conjugated system supramolecular sensor Because Arg plays a crucial role in many biological functions, we also investigated the application characteristics of HGP5-based fluorescence sensors in the biological field. We first studied the cytotoxic effects of HGP5 on living cells using MTT assays. For example... Figure 20 As shown, when the incubation concentration reached 75 μmol / L, over 68% of HeLa cells survived, demonstrating that HGP5 exhibits good biocompatibility and low cytotoxicity in live cells. Subsequently, we used fluorescence microscopy to detect and record the fluorescence images of HGP5 capturing Arg in live cells. According to the testing requirements, cells under bright field were used as a blank control, such as... Figure 21 As shown in Figure a, the cells have regular morphology and are in good growth condition. Subsequently, we collected fluorescence images recorded by fluorescence microscopy, as shown below. Figure 21 As shown in b, we used 370nm wavelength excitation and observed weak fluorescence in the cytoplasm of HeLa cells, which can be applied as a fluorescent in vivo imaging probe in the cellular microenvironment. Upon further addition of the target substance Arg, strong fluorescence was observed within the cells, as shown in [example image]. Figure 21 As shown in d, this demonstrates that HGP5 can capture Arg in live cells. It also shows its potential application in live cell analysis.

[0018] III. HGP5 sensor detects Al 3+ Application 1. Chemical sensor HGP5 identifies Al 3+ In the chemical sensor, HGP5 was in a solution of DMSO / H2O (v:v=9:1) system (C HGP5 =2×10 -5 Add Al to M) respectively 3+ Ag + Ba 2+ Ca 2+ Cd 2+ Co 2+ Cr 3+ La 3+ Fe 3+ Eu 3+ Hg 2+ Cu 2+ Mg 2+ Ni 2+ Pb 2+ 、Tb 3+ Zn 2+Observe the changes in the fluorescence of the solution. Figure 22 The fluorescence spectra (λ) of different metal cations added to the solution of the sensor molecule HGP5 in the DMSO: H2O (v: v=9: 1) system of this invention are shown. ex =370 nm). The results showed that only Al 3+ The addition of Al cations activated the fluorescence in the DMSO:H2O (v:v=9:1) solution of the HGP5 fluorescence sensor. However, the addition of other metal cations did not activate the fluorescence in the DMSO:H2O (v:v=9:1) solution of the HGP5 fluorescence sensor. We found that the addition of Al cations... 3+ Afterwards, the fluorescence of HGP5 turned blue and underwent a blue shift, while the addition of other metal ions had little effect on its fluorescence intensity.

[0019] Fluorescent titration experiments showed that the HGP5 sensor is effective for Al 3+ The lowest detection limit is 7.94 × 10⁻⁶. -9 M (as) Figure 23 , 24 (As shown). Much smaller than Al in drinking water. 3+ The maximum concentration setting.

[0020] 2. Al 3+ Assembly performance study of HGP5 In order to study Al 3+ Regarding the assembly performance of HGP5, we... 1 H NMR was used to study its assembly mechanism, such as Figure 25 As shown, in 1 In the 1H NMR titration spectrum, H on the column aromatic hydrocarbon a H b With Al 3+ The addition of H gradually shifts to a lower field and disappears, while H c H d A high-field displacement occurred. This indicates that Al 3+ Complexes are formed at the phenolic hydroxyl and acylhydrazone positions and enter the cavity of the columnar aromatic hydrocarbon, with cation-π and multiple coordination interactions between the host and guest. Furthermore, FT-IR spectroscopy (…) Figure 26 This indicates that adding Al 3+ Subsequently, the tensile vibration absorption peaks of OH and NH in HGP5 increased, a phenomenon that confirms the presence of Al. 3+ It exhibits strong multiple coordination interactions with phenolic hydroxyl and acylhydrazone groups, and this is related to... 1 The results of the 1H NMR (400 MHz) titration were consistent, revealing that Al 3+ The mechanism of interaction with HGP5 was investigated. The morphological structure before and after assembly was evaluated using scanning electron microscopy. Figure 27 HGP5 was observed to have a regular spherical structure. Figure 27 (a)), however, when Al is added 3+ Afterwards, they formed a regular-looking rhomboid sheet-like structure stacked together. Figure 27 (b) indicates that Al 3+ The interaction with the HGP5 host-guest pair resulted in significant morphological changes.

[0021] 6. Based on the chemical sensor HGP5, Al in living cells 3+ Research on detection We studied Al 3+ The detection capability of the sensor in living cells. We first investigated the cytotoxic effect of HGP5 on living cells using the MTT assay. We found that HGP5 exhibits good biocompatibility and low cytotoxicity in living cells. Figure 20 We then used fluorescence microscopy to detect and record the effect of HGP5 in capturing Al in live cells. 3+ Fluorescence images. According to the testing requirements, cells under bright field were used as a blank control, such as... Figure 28 As shown in Figure a, the cells have regular morphology and are in good growth condition. Subsequently, we collected fluorescence images recorded by fluorescence microscopy, as shown below. Figure 28 As shown in b, we used 370nm wavelength excitation and observed weak fluorescence in the cytoplasm of HeLa cells, which can be applied as a fluorescent in vivo imaging probe in the cellular microenvironment. Further addition of the target substance Al... 3+ The cells emit strong fluorescence, such as Figure 28 As shown in d, this demonstrates that HGP5 can capture Al in living cells. 3+ Therefore, this sensor can be used as a bioimaging probe to detect Al in cells. 3+ .

[0022] In summary, this invention introduces a large conjugated system into the design of a columnar aromatic hydrocarbon-based chemical sensor to improve its signal response capability to host-guest interactions. Simultaneously, it introduces acylhydrazones to functionalize the conjugated columnar aromatic hydrocarbons, utilizing the synergistic effect between the acylhydrazone and the columnar aromatic hydrocarbon to enhance the selective binding capability to the target guest. This type of columnar aromatic hydrocarbon can firstly improve the selectivity and sensitivity to the guest through the synergistic effect between the cavity and the acylhydrazone group; secondly, its large conjugated structure can effectively enhance intramolecular charge transfer, thereby improving its optical response signal. In this invention, the sensor molecule HGP5 can detect Arg (lowest detection limit under fluorescence: 3 × 10⁻⁶) using both colorimetric and fluorescence dual-channel detection. -8 M, Limit of detection under UV light: 2.99 × 10 -8 M), and can also detect Al with ultrasensitive fluorescence. 3+ (Lowest detection limit under fluorescence: 7.94 × 10⁻⁶)-9 M). Furthermore, this chemical sensor also has potential applications in cell imaging, as it can detect Al in cells. 3+ And Arg. This invention is for the development of a method to detect Arg and Al in aqueous solutions. 3+ Novel supramolecular fluorescent materials offer a new approach. Attached Figure Description

[0023] Figure 1 This is the hydrogen spectrum of the sensor intermediate 1 of the present invention; Figure 2 This is the carbon spectrum of the sensor intermediate 1 of the present invention; Figure 3 This is the mass spectrum of the sensor intermediate 2 of the present invention; Figure 4 This is the hydrogen spectrum of the sensor intermediate 2 of the present invention; Figure 5 This is the carbon spectrum of the sensor intermediate 2 of the present invention; Figure 6 This is the mass spectrum of the HGP5 sensor of the present invention; Figure 7 The hydrogen spectrum of the HGP5 sensor of this invention; Figure 8 The carbon spectrum of the HGP5 sensor of this invention; Figure 9 The fluorescence response spectra (A) and fluorescence photographs (B) at 365 nm of the HGP5 sensor of the present invention after adding different amino acids to a DMSO / H2O (v: v=9: 1) solution are shown. Figure 10 The UV response spectra (A) and photographs (B) of the sensor HGP5 of this invention under natural light after adding different amino acids to a DMSO / H2O (v: v=9:1) solution. Figure 11 The image shows a fluorescence titration experiment of Arg added to the DMSO / H2O (v: v=9:1) solution of the sensor HGP5 of this invention; Figure 12 The fluorescence linear fitting diagram of Arg added to the DMSO / H2O (v: v=9:1) solution of the sensor HGP5 of this invention; Figure 13 The image shows a UV titration experiment of Arg added to the DMSO / H2O (v: v=9:1) solution of the sensor HGP5 of this invention; Figure 14 The ultraviolet radiation fitting graph of Arg added to the DMSO / H2O (v: v=9: 1) solution of the sensor HGP5 of this invention; Figure 15The 1H NMR spectra of the sensor HGP5 of this invention with different equivalents of Arg added to DMSO solution; Figure 16 The assembly mechanism of the HGP5+Arg sensor of this invention; Figure 17 This is a scanning electron microscope image of the HGP5 and HGP5+Arg sensors assembled according to the present invention; Figure 18 This is a test paper for detecting Arg at different concentrations using the HGP5 sensor of the present invention; Figure 19 This is the standard curve for quantitative detection of Arg by the HGP5 sensor of this invention; Figure 20 The results of the MTT assay for the HGP5 sensor of this invention in HeLa cells; Figure 21 These are fluorescence imaging images of the HGP5 sensor of the present invention in HeLa cells; (a) cell image under bright field; (b) fluorescence image after HGP5 addition; (c) blank control under dark field; (d) fluorescence image after HGP5 and Arg addition; Figure 22 The fluorescence response spectra (A) and fluorescence photographs (B) at 365 nm of the HGP5 sensor of the present invention with different metal ions added to a DMSO / H2O (v: v= 9: 1) solution are shown. Figure 23 Al was added to the DMSO / H2O (v:v=9:1) solution of the sensor HGP5 of this invention. 3+ A diagram of a fluorescence titration experiment; Figure 24 Al was added to the DMSO / H2O (v:v=9:1) solution of the sensor HGP5 of this invention. 3+ The fluorescence linear fitting plot; Figure 25 Different equivalents of Al were added to the DMSO solution of the sensor HGP5 of this invention. 3+ The hydrogen NMR spectrum; Figure 26 The present invention relates to sensors HGP5 and HGP5+Al. 3+ The infrared spectrum after assembly; Figure 27 The present invention relates to sensors HGP5 and HGP5+Al. 3+ Scanning electron microscope image after assembly; Figure 28 The images show fluorescence imaging of the HGP5 sensor of this invention in HeLa cells: (a) Cell image under bright field; (b) Fluorescence image after HGP5 addition; (c) Blank control under dark field; (d) Cell image after HGP5 and Al addition.3+ Fluorescent images. Detailed Implementation

[0024] The following specific embodiments illustrate the synthesis and detection of Arg and Al by the HGP5 sensor of the present invention. 3+ The application will be further explained.

[0025] Example 1: Synthesis of the chemical sensor HGP5 (1) Synthesis of methyl di-m-benzoate-functionalized conjugated column[5] aromatic 1: OTf-EtP[5] (1.10 g, 1.0 mmol), 3-methoxycarbonylphenylboronic acid (900.0 mg, 5.0 mmol), Na2CO3 (650.0 mg, 5.0 mmol) and Pd(PPh3)4 (300.0 mg, 0.26 mmol) were added to a 100 mL two-necked flask and reacted at 80 °C for 36 h under nitrogen protection with 60 mL THF:H2O (v: v=5:1) as solvent. After the reaction was completed, water (50 mL) was added and extracted with ethyl acetate (3 × 100 mL). The combined organic phases were concentrated and the residue was subjected to column chromatography (petroleum ether: ethyl acetate = 50:1, v / v) to obtain a white solid, which is methyl di-m-benzoate-functionalized conjugated column[5] aromatic 1 (0.51 g). Yield: 51%; Melting point: 167-168℃.

[0026] (2) Synthesis of bis-benzoylhydrazine-functionalized conjugated column[5]arene 2: hydrazine hydrate (37.55 mg, 0.75 mmol) and bis-benzoylhydrazine-functionalized conjugated column[5]arene 1 (321 mg, 0.3 mmol) were added to 20 mL of anhydrous ethanol and reacted at 80 °C for 24 h. After the reaction was completed, a white solid was precipitated. The solid was filtered and washed with ethanol. The product obtained was bis-benzoylhydrazine-functionalized conjugated column[5]arene 2 (202 mg, 63%).

[0027] (3) Synthesis of A, A'-dihydroxynaphthylhydrazone-functionalized conjugated column[5] aromatic HGP5: (107.1 mg, 0.1 mmol)2 and (43.03 mg, 0.25 mmol)2-hydroxynaphthaldehyde were added to 20 mL of anhydrous methanol and reacted at 70 °C for 24 h. After the reaction was completed, a green solid was precipitated. The solid was filtered and washed with ethanol. The product obtained was the fluorescent colorimetric dual-channel conjugated system sensor HGP5 (94 mg, 68%).

[0028] Example 2: HGP5 chemical sensor for dual-channel fluorescence colorimetric recognition of Arg Transfer 2 mL of a DMSO:H2O (v:v=9:1) solution of sensor molecule HGP5 (C=2×10⁻⁶) to each sample.-5 In a series of fluorescent cuvettes, aqueous solutions of Arg, Gly, Phe, Asn, Thr, Met, Ile, Leu, Ser, His, Trp, Ala, Gln, Glu, Asp, Pro, Lys, Val, and Cys (C=0.1M) were added, respectively. If the fluorescence of the DMSO / H2O solution in the HGP5 fluorescence sensor turned on and the solution color changed to orange-yellow, it indicated that Arg had been added. If the fluorescence of the DMSO / H2O solution in the HGP5 sensor did not change, it indicated that Arg had not been added.

[0029] To further investigate the sensitivity of HGP5 for Arg detection in DMSO / H2O, we conducted a fluorescence titration experiment. The fluorescence emission intensity of HGP5 gradually increased with increasing Arg concentration. Based on these results, we also plotted the corresponding fitting curve and calculated the limit of detection (LOD) of HGP5 for Arg using the 3δ / S method, which was 3 × 10⁻⁶. -8 M. To further investigate the sensitivity of HGP5 for the naked-eye recognition of Arg in DMSO-H2O, we conducted a UV titration experiment. The UV absorption intensity of HGP5 gradually increased with increasing Arg concentration. Based on the above results, we also plotted the corresponding fitting curve and calculated the limit of detection (LOD) of HGP5 for Arg to be 2.99 × 10⁻⁶. -8 M.

[0030] Example 3: The chemical sensor HGP5 exhibits ultrasensitive identification of Al under fluorescence. 3+ Transfer 2 mL of a DMSO:H2O (v:v=9:1) solution of sensor molecule HGP5 (C=2×10⁻⁶) to each sample. -5 M) Add Al to a series of fluorescent cuvettes respectively 3+ Ag + Ba 2+ Ca 2+ Cd 2+ Co 2+ Cr 3+ La 3+ Fe 3+ Eu 3+ Hg 2+ Cu 2+ Mg 2 + Ni 2+ Pb 2+ 、Tb 3+ Zn 2+The fluorescence of the solution was observed using an aqueous solution (C=0.1M). If the fluorescence sensor HGP5 activated with a DMSO / H2O solution and emitted blue fluorescence, it indicates that Al was added. 3+ If the fluorescence of the DMSO / H2O solution in sensor HGP5 does not change, it indicates that Al was not added. 3+ .

[0031] To further investigate the effect of HGP5 on Al in DMSO / H2O 3+ To assess the detection sensitivity, we conducted a fluorescence titration experiment. The fluorescence emission intensity of HGP5 increased with Al... 3+ The effect of increasing concentration gradually strengthens. Based on the above results, we also plotted the corresponding fitting curve and used the 3δ / S method to calculate the effect of HGP5 on Al. 3+ The limit of detection (LOD) for fluorescence is 7.94 × 10⁻⁶. -9 M.

Claims

1. An A,A'-dihydroxynaphthoylhydrazone-functionalized conjugated columnar aromatic hydrocarbon HGP5, the structural formula of which is: 。 2. The method for synthesizing A,A'-dihydroxynaphthoylhydrazone-functionalized conjugated column [5] aromatic hydrocarbon HGP5 as described in claim 1, comprising the following steps: (1) Synthesis of methyl di-m-benzoate-functionalized conjugated column[5] aromatics: OTf-EtP[5] and 3-methoxycarbonylphenylboronic acid were used as substrates, and THF / H2O mixture was used as solvent. Na2CO3 and Pd(PPh3)4 were added and reacted at 75~85℃ for 30~40h under nitrogen protection. After the reaction was completed, water was added and extracted with ethyl acetate. The combined organic phases were concentrated, and the residue was subjected to column chromatography to obtain a white solid, which is methyl di-m-benzoate-functionalized conjugated column[5] aromatics. The structural formula of OTf-EtP[5] is ; (2) Synthesis of bis-m-benzoylhydrazine-functionalized conjugated column[5] aromatics: using hydrazine hydrate and methyl bis-m-benzoate-functionalized conjugated column[5] aromatics as substrates and anhydrous ethanol as solvent, the reaction was carried out at 75~85℃ for 20~25h. After the reaction was completed, a white solid was precipitated. The solid was filtered and washed with hot ethanol. The product obtained was bis-m-benzoylhydrazine-functionalized conjugated column[5] aromatics. (3) Synthesis of A, A'-dihydroxynaphthoylhydrazone-functionalized conjugated column[5] aromatic HGP5: using bis-m-benzoylhydrazine-functionalized conjugated column[5] aromatic and 2-hydroxynaphthoaldehyde as substrates, and anhydrous methanol as solvent, the reaction was carried out at 60~80℃ for 20~24h. After the reaction was completed, a green solid was precipitated. The solid was filtered and washed with ethanol. The product obtained was A, A'-dihydroxynaphthoylhydrazone-functionalized conjugated column[5] aromatic HGP5.

3. The method for synthesizing A,A'-dihydroxynaphthoylhydrazone-functionalized conjugated column [5] aromatic hydrocarbon HGP5 as described in claim 2, characterized in that: In step (1), the molar ratio of OTf-EtP[5] to 3-methoxycarbonylphenylboronic acid is 1:5; in the THF / H2O mixture, the volume ratio of THF to H2O is 5:

1.

4. The method for synthesizing A,A'-dihydroxynaphthoylhydrazone-functionalized conjugated column [5] aromatic hydrocarbon HGP5 as described in claim 2, characterized in that: In step (2), the molar ratio of the conjugated column[5] aromatic hydrocarbon and hydrazine hydrate functionalized with methyl di-m-benzoate is 1:2 to 1:

3.

5. The method for synthesizing A,A'-dihydroxynaphthoylhydrazone-functionalized conjugated column [5] aromatic hydrocarbon HGP5 as described in claim 2, characterized in that: In step (3), the molar ratio of the bis-benzoylhydrazine-functionalized conjugated columnar aromatic hydrocarbon [5] and 2-hydroxynaphthaldehyde is 1:2 to 1:

3.

6. The application of the A, A'-dihydroxynaphthoylhydrazone-functionalized conjugated column[5]arene HGP5 as described in claim 1 in the detection of Arg for non-disease diagnosis and treatment purposes.

7. The application as described in claim 6, characterized in that: In the DMSO / H2O solution of HGP5, Arg, Gly, Phe, Asn, Thr, Met, Ile, Leu, Ser, His, Trp, Ala, Gln, Glu, Asp, Pro, Lys, Val, and Cys were added respectively. Only the addition of Arg enabled the fluorescence of HGP5 to be activated, and the HGP5 solution turned orange-yellow. Therefore, Arg can be identified by colorimetric fluorescence dual-channel recognition. In the DMSO / H2O solution, the volume ratio of DMSO to H2O is 9:

1.

8. The A,A'-dihydroxynaphthoylhydrazone functionalized conjugated column[5] aromatic HGP5 described in claim 1 is used for non-disease diagnosis and treatment purposes in the detection of Al 3+ Applications in [the field].

9. The application as described in claim 8, characterized in that: Al was added to the DMSO / H2O solution of HGP5. 3+ Ag + Ba 2+ Ca 2+ Cd 2+ Co 2+ Cr 3+ La 3+ Fe 3+ Eu 3+ Hg 2+ Cu 2+ Mg 2+ Ni 2+ Pb 2+ 、Tb 3+ Zn 2+ Only Al 3+ The addition of [a specific ingredient] enables the fluorescence of HGP5 to turn on and undergo a blue shift, thus achieving [the desired effect] on Al. 3+ The fluorescence ultrasensitive detection; in the DMSO / H2O solution, the volume ratio of DMSO to H2O is 9:

1.

10. The application of the A, A'-dihydroxynaphthoylhydrazone-functionalized conjugated column[5] aromatic hydrocarbon HGP5 as described in claim 1 in the preparation of cell fluorescence imaging detection reagents.

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