CN108070092B - Supermolecular gel based on functionalized column [5] arene and application thereof in identifying iron ions and L-Cys - Google Patents

Abstract

The invention discloses a supramolecular gelator MP5 based on naphthalimide functionalized column 5 aromatic hydrocarbon, wherein the gelator can form an organic supramolecular gel MP5-G with yellow aggregation state induced fluorescence through pi-pi action in cyclohexanol solution, and the organic supramolecular gel can detect Fe with high selectivity and ultra-sensitivity³⁺: adding Fe into MP5-G respectively³⁺，Hg²⁺，Ag⁺，Ca²⁺，Cu²⁺，Co²⁺，Ni²⁺，Cd²⁺，Pb²⁺，Zn²⁺，Cr³⁺，Mg²⁺Plasma of only Fe³⁺The fluorescence was quenched and a stable metal gel MP5-FeG was formed. When L-Cys is added to a fluorescence-quenched metal gel, the L-Cys is associated with Fe³⁺The complexation restores the pi-pi action between MP5-G again, which leads to the reappearance of aggregation state induced fluorescence, thereby realizing the aim of Fe³⁺And continuous reversible ultrasensitive detection of L-Cys.

Description

Supermolecular gel based on functionalized column [5] arene and application thereof in identifying iron ions and L-Cys

Technical Field

The invention relates to a column [5] based on functionalization]Aromatic super-molecular organogel, in particular to a column [5] based on functional bis-naphthalimide]Aromatic supramolecular gels; the invention also relates to the single selective fluorescent recognition of Fe by the supermolecular organogel³⁺And continuityAn application of identifying cysteine L-Cys belongs to the field of organogel.

Background

Organogels are supramolecular (soft) materials formed by self-assembly of low molecular weight organic compounds (gelators) in organic solvents through weak intermolecular interactions such as hydrogen bonding, van der waals forces, pi-pi stacking effects, and the like. This material has the specific advantages of both solid and liquid materials: the gel molecules keep the chemical properties of the gel molecules, can perform some reactions in the solution, and meanwhile, the gel material has the advantages of stability similar to a solid, such as easy storage and the like, so the gel material has wide application in the field of supramolecular soft materials.

Iron element is a trace element which is widely existed in natural environment and is necessary for human body, animals and plants, and is an important component for composing hemoglobin, myoglobin and various enzymes, if the body lacks iron, the synthesis of hemoglobin and myoglobin can be influenced, and the activity of some enzymes such as cytochrome C, ribonucleotide reductase, succinate dehydrogenase and the like can be reduced. These enzymes are closely related to biological oxidation, tissue respiration, and decomposition and synthesis of neurotransmitters. Therefore, iron deficiency can cause many physiological changes, which can lead to various diseases such as low immunity, intelligence reduction, body infection resistance reduction, body temperature regulation capacity influence, nerve dysfunction, work efficiency reduction and the like, and most commonly iron deficiency anemia. The special properties of the material also have a plurality of influences on the chemical production process. Therefore, there has been much interest in developing analytical methods for determining the iron content of substances. In order to be able to detect and monitor iron ions, an efficient method is needed. Among various methods for detecting iron ions, fluorescence detection has been receiving more and more attention due to its characteristics of high sensitivity and easy operation.

Amino acid, one of the numerous bioactive macromolecules for constructing living organisms, is a basic material for constructing cells and repairing tissues. Amino acids are used by the human body to make antibody proteins to combat bacterial and viral infections, hemoglobin to deliver oxygen, enzymes and hormones to maintain and regulate metabolism. The amino acid can provide energy for the activities of the organism and the brain, and is a source of all lives. Its detection is important. In particular to L-cysteine (L-Cys), which is an amino acid antidote, participates in the reduction process of cells and the phospholipid metabolism in the liver, and has the pharmacological effects of protecting liver cells from being damaged, promoting the recovery of liver functions and promoting the exuberance. It is mainly used for treating radiopharmaceuticals poisoning, heavy metal poisoning, and antimonide poisoning, and can also be used for treating hepatitis, toxic hepatitis, seropathy, etc., and preventing liver necrosis. Therefore, there has been much interest in developing an assay method that can rapidly and sensitively measure the content of L-cysteine in an environment.

Pillar arenes have attracted a great deal of attention in supramolecular chemistry in recent years as a new class of macrocyclic molecular hosts. Although a pillar arene is structurally similar to a traditional macrocyclic molecule, it has unique advantages. First, it has better symmetry and regularity than crown ethers, cyclodextrins, calixarenes, and this particular structure makes them uniquely selective for guests; second, the pillared arenes are more easily functionalized by substituents at both ends of the benzene ring than other types of hosts; third, the column aromatics are a good necessary complement to the traditional host. Many properties in terms of host-guest complexation have been investigated in terms of symmetric pillar arene. Nevertheless, the study of column [5] arene supramolecular organogels based on bis-naphthalimide functionalization remains a major challenge. In addition, relatively few supramolecular column arene gel documents report pi-pi stacking as a driving force.

Disclosure of Invention

The invention aims to provide a supramolecular organogel based on bis-naphthalimide functionalized column [5] arene;

another object of the present invention is to provide the use of the supramolecular organogel in single selective fluorescence continuous recognition of iron ions and cysteine

Supramolecular organogel based on bis-naphthalimide functionalized column [5] arene

The supermolecule organogel takes column [5] arene based on functional bis-naphthalimide as a gel factor, and is fully dissolved into cyclohexanol under heating to obtain a transparent solution; upon cooling to room temperature, a stable, condensed yellow gel was formed, labeled MP 5-G.

The mass-to-volume ratio of the gel factor (marked as MP5) to the cyclohexanol is 50-60 mg/ml.

Experiments show that the organogel has good stability, and the shape of the organogel is kept unchanged after the organogel is placed for several days. The resolubilization temperature of the organic gel OG is 43-45 ℃.

The structural formula of the gelator is as follows:

。

FIG. 1 shows the change of fluorescence intensity of MP5-G with temperature (lambda) during gel formation_ex=375 nm). The results in FIG. 1 show that MP5-G is not fluorescent in the sol state (MP 5-Gsol), and as the temperature is lowered, the sol turns into a gel, producing strong yellow aggregate fluorescence (MP 5-Ggel).

In order to investigate the presence of the gelator MP5, it was examined by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) (cyclohexanol was the solvent). SEM was performed under conditions in which the organogel was vacuum dried and then subjected to a gold-spraying treatment. As a result, the organogel was found to exist in a spherical form (see FIG. 8 b), and the transmission electron microscope was confirmed to be a solid sphere.

Identification experiment of di-and supramolecular organogel MP5-G on cations

1. MP5-G vs. Fe³⁺Fluorescence response of

A small amount (about 0.01G) of each organogel MP5-G was taken in 18 parts on a white spot plate, and each organogel was added with 5 times equivalent of a different cation (C =0.1moL/L, Mg)²⁺，Ca²⁺，Cr³⁺，Fe³⁺，Co²⁺，Ni²⁺，Cu²⁺，Zn²⁺，Ag⁺，Cd²⁺，Hg²⁺，Pb²⁺，Ba²⁺，Al³⁺，La³⁺，Eu³⁺) An aqueous solution of (a).The gel was then observed for fluorescent color change under an ultraviolet lamp. The results show that organogels encounter Fe³⁺The color of the solution changes from yellow to black, while the organogel does not change when encountering solutions containing other ions. Therefore, the organic gel OG can specifically and selectively recognize Fe through fluorescence³⁺。

Meanwhile, when the organic gel MP5-G is added with Fe³⁺When the sample to be detected is solid, the sample to be detected can be directly dissolved to realize the detection of iron ions, so that the detection process of the sample is simplified. Therefore, the use of the material greatly simplifies the detection method of iron ions and reduces the detection cost.

2. Organogels MP5-G vs. Fe³⁺Fluorescence titration experiment of

Preparing a 200 mu L (gel concentration is 50mg/mL) MP5-G portion in a micro-fluorescence colorimetric pool, and adding different equivalent Fe into MP5-G³⁺The change in fluorescence intensity of the gel was measured in an aqueous solution (C =0.1 moL/L). As shown in fig. 2, with Fe³⁺With gradual addition, the fluorescence at 535nm gradually decreases and eventually stabilizes. And MP5-G vs Fe³⁺The detection limit of the fluorescence spectrum of (1.44X 10)^-8And M, the detection limit is very low, and the level of ultra-sensitive detection is achieved. The MP5-G can detect Fe with ultra-sensitivity in the environment³⁺。

Third, identification experiment of metal gel to amino acid

1. Preparation of Metal gels

The gel factor MP5 and ferric perchlorate hexahydrate are heated and dissolved in cyclohexanol, and after being cooled to room temperature, stable metal organic gel is formed and is marked as MP 5-FeG. The molar ratio of the gelator to the iron perchlorate hexahydrate is 1: 5. Experiments show that the organic metal gel has good stability, and the shape of the gel is kept unchanged after the organic metal gel is placed for several days.

2. Amino acid recognition experiment of metal gel (MP 5-FeG)

2.1 fluorescent response of MP5-FeG to L-Cys

A small amount (about 0.01g) of 21 parts of each metal gel MP5-FeG was added to a white spot plate, and 5 times the amount of each metal gel was added to the plateEquivalent amounts of different amino acids (C =0.1moL/L, L-Phe, L-Gln, L-Ile, L-Thr, L-Glu, β -Ala, L-Ser, L-Met, L-Val, L-Tyr, L-Arg, DL-Asp, L-Pro, L-His, L-Leu, L-Gly, L-Trp, L-Lys, L-Asn and L-Cys). The gel was then observed for fluorescent color change under an ultraviolet lamp. As a result, it was found that the fluorescence of the metal gel FeG was turned on when it was exposed to the aqueous cysteine solution, and the color of the metal gel changed from black to yellow under the excitation wave of 365nm, indicating Fe³⁺The complex is competed by cysteine, so that the color of the metal gel is restored to yellow of the gel factor from black. While aqueous solutions of other amino acids encounter the metal gel without changing its color. Therefore, the metal gel MP5-FeG can specifically and selectively carry out fluorescence recognition on L-Cys in aqueous solution.

2.2 titration experiment of MP5-FeG against L-Cys

A200. mu.L volume of MP5-FeG (gel concentration of 50mg/mL) was prepared in a microfluorescent cuvette, to which was added aqueous solutions of different equivalents of L-Cys (C =0.1moL/L), and the change in fluorescence intensity of the gel was measured as the L-Cys was gradually added, the fluorescence at 475 nm gradually increased and eventually stabilized, as shown in FIG. 3. And the detection limit of MP5-FeG on the fluorescence spectrum of L-Cys is 1.2 multiplied by 10^-8M (FIG. 4), indicating that MP5-FeG can detect L-Cys with ultra-sensitivity in the environment.

IV, MP5-G vs Fe³⁺And the mechanism of continuous recognition of L-Cys

For MP5-G vs Fe³⁺And the mechanism of continuous recognition of L-Cys, we pass¹NMR, IR, XRD, SEM, EIS-MS were studied.¹NMR (see FIG. 5) showed that as the amount of the gel factor MP5 increased, hydrogen on the benzene ring moved to the high field and hydrogen on the naphthalene ring also moved to the high field, indicating that there was strong pi-pi stacking between the naphthalene rings on the MP5 molecule. IR (FIG. 6) shows that the peak of carbonyl stretching vibration hardly changes much after MP5 forms MP 5-G; when adding Fe into MP5-G³⁺The carbonyl stretching vibration peak is moved to a low wave number; further addition of L-Cys to MP5-FeG resulted in the recovery of the carbonyl stretch oscillation peak to the position of MP 5-G. XRD showed (see FIG. 7) that there was pi-pi stacking during MP5 formation into MP5-G, and Fe was added³⁺Can result inThe characteristic peak of pi-pi stacking disappears, and the addition of L-Cys can cause the characteristic peak of pi-pi stacking to reappear. SEM (see FIG. 8) shows that the formation of MP5-G from MP5 results in the transformation of the compound form from an amorphous structure to a spherical structure, and the addition of Fe³⁺The morphology is transformed into a blocky structure, and the addition of L-Cys results in the morphology being restored again to a structure similar to MP 5-G. EIS-MS (FIG. 9) showed that MP5 was associated with Fe³⁺The complexation ratio of (a) to (b) is 1: 1.

In conclusion, the super-sensitive recognition process of the organic supramolecular polymer gel MP5-G is realized by the novel pi-pi action and the competition of cation-pi. (FIG. 10) when Fe was added to MP5-G³⁺Due to Fe³⁺Can generate cation-pi action with naphthalimide, and damage pi-pi action between gel factors, so that fluorescence quenching of MP5-G is caused; when L-Cys was added to fluorescence-quenched metal gel MP5-FeG, the addition was due to L-Cys and Fe³⁺The complexation restores the pi-pi action between MP5-G again, which leads to the reappearance of aggregation state induced fluorescence, thereby realizing the aim of Fe³⁺And continuous reversible ultrasensitive detection of L-Cys.

Drawings

FIG. 1 shows the change of fluorescence intensity of MP5-G with temperature (lambda) during gel formation_ex=375 nm)。

FIG. 2 shows MP5-G vs. Fe³⁺Fluorescence titration of (lambda)_ex=375 nm)。

FIG. 3 is a fluorescent titration (. lamda.) of MP5-FeG against L-Cys_ex=375 nm)。

FIG. 4 is a curve fitted to MP5-FeG versus L-Cys.

FIG. 5 is a concentration NMR spectrum of the gel factor MP 5.

FIG. 6 shows IR spectra of gelator MP5, organogel MP5-G, metal gel MP5-FeG and MP5-FeG + L-Cys.

FIG. 7 is an XRD pattern of gelator MP5, organogel MP5-G, metal gel MP5-FeG and MP5-FeG + L-Cys.

FIG. 8 is the scanning electron micrographs of gelator MP5 (a), organogel MP5-G (b), metal gel MP5-FeG (c) and the binding of metal gel and L-Cys (d).

FIG. 9 shows gelatorsMP5 and Fe³⁺Mass spectrum after complexation.

FIG. 10 is a graph showing the possible self-assembly and continuity of the gelator MP5 to identify Fe³⁺And the L-Cys mechanism.

Detailed Description

The synthesis of the supramolecular organogelator MP5 of the invention and the identification of Fe by single selection are described in the following by specific examples³⁺The method of L-Cys is further described.

Example 1 Synthesis of supramolecular organogelator MP5

(1) Synthesis of intermediate (ZM): to a 500mL round bottom flask were added hydroquinone (2.2022 g, 20.0mmol), anhydrous potassium carbonate (16.56 g, 120 mmol), potassium iodide (6.64 g, 40mmol), 1, 6-dibromohexane (39.035g, 160 mmol) and 400 mL acetone, respectively, and heated under nitrogen (65 ℃ C.) under reflux and stirred for three days. And after the reaction is finished, performing suction filtration, adding silica gel, stirring, performing spin drying, and purifying by using a column chromatography (petroleum ether: ethyl acetate =50:1) to obtain a white product, namely ZM. Yield: 80%, melting point: 97-102 ℃.¹H NMR (600 MHz, Chloroform-d) /ppm： 6.81 (s, 4H), 3.90(t, 4H), 3.42 (t,4H), 1.89 (m, 4H), 1.77 (m, 4H), 1.49 (m, 8H).¹³C NMR(CDCl₃，151 MHz)，/ppm：153.14，115.39，68.35，33.79, 32.68, 29.19, 27.92, 25.29。ESI-MS m/z: [ZM+H]⁺Calcd for C₁₈H₂₉Br₂O₂, 437.05; Found 437.01。

(2) Double bromo functionalized column [5]]Synthesis of aromatic hydrocarbon (CP 5): a250 mL round-bottom flask was charged with 1, 4-dibromohexyloxybenzene (1.9g, 5mmol), 1, 4-dimethoxybenzene (2.76 g, 20 mmol), paraformaldehyde (0.75 g, 25mmol) and 1, 2-dichloroethane (200 mL), and the mixture was stirred at room temperature for 30min, then, boron trifluoride ether (6.75 mL) was added and stirred with heating (30 ℃ C.) for 60 min. After the reaction is finished, adding water to stop the reaction, stirring at room temperature for 15min, then extracting and washing with dichloromethane and water, drying with anhydrous sodium sulfate, filtering, adding silica gel to mix, spinning, and purifying by column chromatography (petroleum ether: ethyl acetate =50:1) to obtain a white product, namely CP 5. Yield: 30%, melting point: 185 ℃ and 189 ℃.¹H NMR (600 MHz,Chloroform-d) /ppm：7.01 – 6.84 (m, 10H), 4.04- 3.71 (m, 38H), 1.84 -1.14 (m,20H). ESI-MS m/z: [C₅₅H₆₈O₁₀Br₂+ NH₄ ⁺]calcd for 1066.3493; Found 1066.3496。

(3) Synthesis of 1, 8-naphthalimide glycine (NA): to a 100 mL round bottom flask were added 1, 8-naphthalic anhydride (1.98 g, 10mmol), glycine (1.13 g, 15.0 mmol), and DMF (75 mL), respectively. The mixture was heated (140 ℃) under nitrogen for three days under reflux. After the reaction is finished, cooling to room temperature, adding water, carrying out suction filtration, drying the solid, and then recrystallizing with hexanitrile to obtain the gray powder NA. Yield: 65%, melting point:>300℃；¹H NMR (600 MHz, DMSO-d6) /ppm：13.06 (s, 1H),8.48 (m, 4H), 7.88 (t, 2H), 4.72 (s, 2H). ESI-MS m/z: [2(NA)+Na]⁺Calcd for C₂₈H₁₈N₂NaO₈, 533.0961; Found 533.09。

(4) synthesis of Binaphthalimide functionalized column [5] arene (MP5)

Heating CP5 and 1, 8-naphthalimide glycine in hexanitrile solution (80 ℃) for refluxing for 48h, adding water to force out a product after the reaction is finished, filtering by suction and drying. The resulting product was dissolved in dichloromethane, stirred with silica gel, spun dry and purified by column chromatography (petroleum ether: ethyl acetate =10:1) to give MP5 as a yellow product. Yield: 16.2%, melting point: 70-72 ℃.¹HNMR (600 MHz, Chloroform-d) /ppm： 8.63 (d,J= 7.3 Hz, 4H), 8.24 (d,J= 8.2Hz, 4H), 7.77 (t,J= 7.7 Hz, 4H), 6.87 (m,J= 12.3 Hz, 10H), 4.21 (t,J=6.8 Hz, 4H), 3.77 (m,J= 13.4 Hz, 42H), 1.71 (m,J= 7.9, 7.2 Hz, 4H), 1.58-1.51 (m, 8H), 1.42 (m, 4H).¹³C NMR (151 MHz, DMSO-d ₆) /ppm： 168.42 , 163.44, 150.30 -150.25 (m), 149.56 , 135.30 , 131.76 , 131.52 , 128.00 , 127.96 ,127.88 , 127.85 , 127.74 , 127.68 , 121.74 , 113.68 , 68.06 , 65.38 , 55.78 ,55.74 , 55.70 , 41.57 , 30.09 , 29.48 , 29.35 , 28.39 , 25.75 , 25.52 . ESI-MS m/z: [C₈₃H₈₄O₁₈N₂+ NH₄ ⁺]calcd for 1414.6057; Found 1414.6035。

Example 2 preparation of supramolecular organogel (MP 5-G)

MP5(0.01g, 7.16X 10) was weighed^-6mol) is added into 0.2mL of cyclohexanol, and the cyclohexanol is fully dissolved under heating to obtain transparent solution; upon cooling to room temperature, the solution formed a stable, condensed yellow gel.

Example 3 identification of Experimental Fe by organogels (MP 5-FeG)³⁺

A small amount (about 0.01g) of organogel MP5-FeG was prepared in 18 parts by weight on a white spot plate, and Mg was added to these organogels²⁺，Ca²⁺，Cr³⁺，Fe³⁺，Co²⁺，Ni²⁺，Cu²⁺，Zn²⁺，Ag⁺，Cd²⁺，Hg²⁺，Pb²⁺，Ba²⁺，Al³⁺，La³⁺And Eu³⁺(1 moL/L). The gel was then observed for fluorescent color change under an ultraviolet lamp. The color of the organogel changed from yellow to black, indicating that Fe was added³⁺The color of the solution, organogel, does not change, indicating the addition of an aqueous solution of other ions.

Example 4 continuous identification of Experimental Fe by organogel (MP 5-G)³⁺And L-Cys

A small amount (about 0.1g) of each of 18 parts of organogel was applied to a white spot plate, and Mg was added to each of these organogels²⁺，Ca²⁺，Cr³⁺，Fe³⁺，Co²⁺，Ni²⁺，Cu²⁺，Zn²⁺，Ag⁺，Cd²⁺，Hg²⁺，Pb²⁺，Ba²⁺，Al³⁺，La³⁺And Eu³⁺(1 moL/L). The gel was then observed for fluorescent color change under an ultraviolet lamp. The color of the organogel changed from yellow to black, indicating that Fe was added³⁺Solution, the gel color of the organogel does not change, indicating the addition of an aqueous solution of other ions.

The above-mentioned black metal gel was divided into 21 parts, and aqueous solutions of L-Phe, L-Gln, L-Ile, L-Thr, L-Glu, L-Ala, L-Ser, L-Met, L-Val, L-Tyr, L-Arg, L-Asp, L-Pro, L-His, L-Leu, L-Gly, L-Trp, L-Lys, L-Asn, and L-Cys were dropped thereon, respectively, and it was found that only the addition of L-Cys opened the fluorescence of the organometallic gel, changed the color of the metal gel from black to yellow, and that the color of the metal gel did not change when aqueous solutions of other amino acids were added.

Example 5 preparation of Metal gel (MP 5-FeG)

First, the gel factor MP5(0.01g, 7.16X 10) was weighed^-6mol), then weighing ferric perchlorate hexahydrate (0.0132 g, 2.86X 10)^-5mol) are added into 0.2mL of cyclohexanol solution, heated to dissolve, and after cooling to room temperature, a stable metal organogel (MP 5-FeG) is formed.

Example 6 identification of L-Cys by Metal gel (MP 5-FeG)

A small amount (about 0.01g) of 21 parts of metal gel MP5-FeG was dropped onto a white spot plate, and an aqueous solution (C =0.1moL/L) of L-Phe, L-Gln, L-Ile, L-Thr, L-Glu, L-Ala, L-Ser, L-Met, L-Val, L-Tyr, L-Arg, L-Asp, L-Pro, L-His, L-Leu, L-Gly, L-Trp, L-Lys, L-Asn, L-Cys was dropped onto these metal gels, respectively, and the change in fluorescence color of the gels was observed under an ultraviolet lamp. When the fluorescence of the metal gel is turned on and the color of the metal gel is changed from black to yellow, the aqueous solution of L-Cys is dripped, and when the color of the metal gel is not changed, the aqueous solution of other amino acids is dripped.

Claims (7)

1. A supermolecule organogel based on functionalized column [5] arene takes the column [5] arene based on the functionalization of bis-naphthalimide as a gel factor, and fully dissolves into cyclohexanol under heating to obtain a transparent solution; when cooled to room temperature, a stable condensed yellow gel is formed; the structural formula of the gel factor based on the pillar [5] arene functionalized by the dinaphthalimide is as follows:

。

2. a supramolecular organogel based on functionalized column [5] arenes, as claimed in claim 1, characterized by: the mass-volume ratio of the gel factor to the cyclohexanol is 50-60 mg/ml.

3. A functionalization-based column [5] according to claim 1]Supramolecular organogel of aromatic hydrocarbon for single selective recognition of Fe³⁺The method is characterized in that: adding Mg on the supermolecule organogel²⁺，Ca²⁺，Cr³⁺，Fe³⁺，Co²⁺，Ni²⁺，Cu²⁺，Zn^{2 +}，Ag⁺，Cd²⁺，Hg²⁺，Pb²⁺，Ba²⁺，Al³⁺，La³⁺，Eu³⁺In an aqueous solution of (3), only Fe³⁺The addition of (a) can change the color of the supramolecular organogel from yellow to black, while the addition of other cations cannot change the color of the supramolecular organogel.

4. A functionalization-based column [5] according to claim 1]Continuous recognition of Fe by supramolecular organogel of aromatic hydrocarbon³⁺And L-Cys, characterized in that: adding Mg on the supermolecule organogel²⁺，Ca²⁺，Cr³⁺，Fe³⁺，Co²⁺，Ni²⁺，Cu²⁺，Zn²⁺，Ag⁺，Cd²⁺，Hg²⁺，Pb²⁺，Ba²⁺，Al³⁺，La³⁺，Eu³⁺In an aqueous solution of (3), only Fe³⁺The addition of (2) can change the color of the supermolecule organogel from yellow to black metal gel, while the addition of other cations can not change the color of the supermolecule organogel; then respectively adding aqueous solution of L-Phe, L-Gln, L-Ile, L-Thr, L-Glu, L-Ala, L-Ser, L-Met, L-Val, L-Tyr, L-Arg, L-Asp, L-Pro, L-His, L-Leu, L-Gly, L-Trp, L-Lys, L-Asn and L-Cys on the black metal gel, and finding that only the addition of L-Cys can open the fluorescence of the organic metal gel, the metal gel is changed from black to yellow, and other metal gels are addedThe color of the metal gel does not change when the amino acid is in an aqueous solution.

5. An organic metal gel based on functionalized column [5] arene is prepared by heating and dissolving column [5] arene with a gelator based on bis-naphthalimide functionalization and ferric perchlorate hexahydrate in cyclohexanol, and cooling to room temperature to form stable metal organic gel; the structural formula of the gel factor based on the pillar [5] arene functionalized by the dinaphthalimide is as follows:

。

6. an organometallic gel based on functionalized column [5] arenes according to claim 5, characterized by: the molar ratio of the gelator to the iron perchlorate hexahydrate is 1: 5.

7. Use of a functionalized column [5] arene-based organometallic gel according to claim 5 for the detection of L-Cys, wherein: respectively taking 21 parts of organic metal gel on a white dropping plate, respectively adding aqueous solutions of L-Phe, L-Gln, L-Ile, L-Thr, L-Glu, L-Ala, L-Ser, L-Met, L-Val, L-Tyr, L-Arg, L-Asp, L-Pro, L-His, L-Leu, L-Gly, L-Trp, L-Lys, L-Asn and L-Cys on the organic metal gel, and finding that only the addition of L-Cys can open the fluorescence of the organic metal gel, the gel is changed from black to yellow, and the color of the metal gel is not changed when the aqueous solutions of other amino acids are added.

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