A biphenyl imidazole bridged bis-p column [5] arene supermolecule polymer and preparation and application thereof

Abstract

The application provides an iron ion-induced biphenyl imidazole bridged double pillar [5] arene supramolecular polymer, which can realize the recognition and detection of Fe 3+ Based on the excellent luminescent and metal coordination properties of the biphenyl imidazole bridged double pillar [5] arene supramolecular polymer, a portable determination of iron ion content online analysis platform based on a smart phone is designed by taking a UV lamp as a medium and the smart phone as a detection tool. The detection platform records the change of the fluorescence color of the iron ion-induced biphenyl imidazole bridged double pillar [5] arene supramolecular polymer by using a smart phone, a dark box and a UV lamp, a standard curve of image RGB value and iron ion concentration is established, the concentration of iron ions in a to-be-detected substance is rapidly detected according to the calibration curve, and real-time detection of the iron ions is realized. The method is simple in operation, and solves the problems of cumbersome and expensive instrument detection in the traditional method.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of fluorescence analysis, and relates to a supramolecular polymer and a method for fluorescence detection of Fe 3+ and a supramolecular polymer-based detection device, in particular to a biphenyl imidazole bridged double pillar [5] arene supramolecular polymer with excellent luminescent performance and metal coordination performance and a method for fluorescence detection of Fe 3+ and a supramolecular polymer-based portable Fe 3+ fluorescence detection device. BACKGROUND

[0002] With the rapid development of modern industry, the demand for iron of human beings greatly increases. The most common form of dissolved iron is iron ions. The valence state of iron metal has a great influence on their mobility, bioavailability, chemical interaction and other behaviors. Therefore, qualitative and quantitative determination of iron ions has important practical significance in many fields such as clinical medicine, biology, environment and industry. At present, fluorescence detection technology is widely used in the monitoring of water pollutants due to its short response time and high sensitivity. Therefore, it is necessary to synthesize a fluorescence supersensor for detecting Fe 3+ .

[0003] For on-site analysis, fluorescence detection technology requires sampling from wastewater and monitoring the concentration in the laboratory, and the fluorescence spectrophotometer is large in size and high in manufacturing cost, and is difficult to be used for on-site analysis conveniently. In recent years, as a functional mobile device with simple operation and portability, smart phones provide new development opportunities for on-site analysis of environmental monitoring. The digital camera in the smart phone can act as a detector to convert images into three primary colors RGB (red, green and blue) of the visible spectrum, and then determine the concentration of pollutants in the water sample. Compared with traditional analysis methods which require relatively complex instruments, smart phones have the advantages of fast analysis speed, low cost and portability, which provide a certain driving force for realizing real-time quantitative on-site analysis of the concentration of pollutants in water.

[0004] However, the photographing of smart phones is affected by environmental conditions, and different light conditions, angles of shooting and background colors will affect the detection results. The application combines fluorescence detection technology with smart phones, which not only helps to reduce the influence of external environment, but also can identify the change of fluorescence color of the fluorescence detection material capturing pollutants through the smart phone, convert the RGB value, establish the linear relationship between the concentration of pollutants and the RGB value, and then quickly and effectively realize the purpose of real-time quantitative on-site analysis of the concentration of pollutants. Therefore, it has certain application value to develop a portable fluorescence detection device based on smart phones, which is simple in structure, convenient to carry, small in environmental influence, high in timeliness and wide in application range. SUMMARY

[0005] The purpose of the present application is to provide a biphenyl imidazole bridged double pillar [5] arene supramolecular polymer and a preparation method thereof;

[0006] Another purpose of the present application is to provide the application of the supramolecular polymer in the fluorescence detection of Fe 3+ ;

[0007] Still another purpose of the present application is to provide a portable Fe 3+ fluorescence detection device based on the biphenyl imidazole bridged double pillar [5] arene supramolecular polymer and a method for detecting Fe 3+ by using the detection device. By using the designed detection device, the signal acquisition and data analysis are realized through the photographing of an ordinary smart phone combined with the RGB (red green blue) standardized color system, a database and a model are established, and the fluorescence data of Fe 3+ in an actual water sample are compared with the database and the model, so that the content of Fe 3+ can be rapidly determined offline.

[0008] I. Biphenyl imidazole bridged double pillar [5] arene supramolecular polymer and preparation method thereof

[0009] The biphenyl imidazole bridged double pillar [5] arene supramolecular polymer is formed by self-assembly in a dimethyl sulfoxide solution, taking biphenyl imidazole bridged double pillar [5] arene dimer H2 as the main body and 1,4-bis (6-bromohexyloxy) benzene G2 as the guest;

[0010] The structural formula of the biphenyl imidazole bridged double pillar [5] arene dimer H2 is as follows:

[0011]

[0012] The structural formula of 1,4-bis (6-bromohexyloxy) benzene G2 is as follows:

[0013] .

[0014] The preparation method of the biphenyl imidazole bridged double pillar [5] arene supramolecular polymer is to add a dimethyl sulfoxide solution of G2 to a dimethyl sulfoxide solution of the biphenyl imidazole bridged double pillar [5] arene dimer, and the biphenyl imidazole bridged double pillar [5] arene supramolecular polymer H2-G2 can be formed by self-assembly at room temperature; the molar ratio of the biphenyl imidazole bridged double pillar [5] arene dimer to G2 is 1:1.

[0015] The preparation method of the biphenyl imidazole bridged double pillar [5] arene dimer comprises the following steps:

[0016] (1) p-methoxyphenol and K2CO3 were dissolved in acetone, and KI and 1,4-dibromobutane were dissolved in acetone, respectively, and refluxed at 60-70 °C for 1-2 h, then mixed together, and refluxed at 60-70 °C for 45-50 h, cooled to room temperature, filtered, and the filtrate was concentrated to obtain a crude product, which was purified by column chromatography to obtain 1-(4-bromobutoxy)-4-methoxybenzene. The molar ratio of p-methoxyphenol to 1,4-dibromobutane was 1:2-1:3, the molar ratio of p-methoxyphenol to K2CO3 was 1:3-1:5, and the molar ratio of KI to 1,4-dibromobutane was 1:10-1:12.

[0017] (2) 1-(4-bromobutoxy)-4-methoxybenzene, 1,4-dimethoxybenzene, and paraformaldehyde were dissolved in 1,2-dichloroethane, stirred at room temperature, and then dropwise added with boron trifluoride etherate until the solution color was dark green, and reacted at 25-35 °C for 30 min, and then quenched with water, extracted with 1,2-dichloromethane, dehydrated with anhydrous sodium sulfate, filtered to remove insoluble solids, and the filtrate was concentrated to obtain a crude product, which was purified by column chromatography to obtain a single modified column [5] arene. The molar ratio of 1-(4-bromobutoxy)-4-methoxybenzene to 1,4-dimethoxybenzene was 1:10-1:12, and the mass ratio of 1-(4-bromobutoxy)-4-methoxybenzene to paraformaldehyde was 1:1-1:2.

[0018] (3) The single modified column [5] arene, benzimidazole, KI, and KOH were added to DMF, and refluxed at 60-70 °C for 45-50 h, cooled to room temperature, filtered, and the filtrate was concentrated to obtain a crude product, which was purified by column chromatography to obtain a benzimidazole functionalized column [5] arene. The molar ratio of the single modified column [5] arene to 3-benzimidazole was 1:1-1:2, the molar ratio of the single modified column [5] arene to KI was 1:0.2-1:0.3, and the molar ratio of the single modified column [5] arene to KOH was 1:2-1:3.

[0019] (4) The benzimidazole functionalized column [5] arene and Cu(OAc)2 were added to xylene (10 mL), and refluxed at 130-150 °C for 10-15 h, cooled to room temperature, filtered, and the filtrate was concentrated to obtain a crude product, which was purified by column chromatography to obtain a biphenylbenzimidazole bridged double column [5] arene dimer. The molar ratio of the benzimidazole functionalized column [5] arene to Cu(OAc)2 was 1:1-1:2.

[0020] The preparation method of 1,4-bis(6-bromohexoxy)benzene G2 is as follows: p-hydroxybiphenyl (2.1 g, 20.0 mmol), K2CO3 (8.4 g, 60 mmol), KI (3.3 g, 20 mmol), and 1,6-dibromohexane (12.2 g, 50 mmol) are added to acetone. Under a nitrogen atmosphere, the reaction mixture is refluxed and stirred at 60-70 °C for 45-50 h. After filtering out the solid, the solvent is evaporated, and the residue is dissolved in CH2Cl2. Column chromatography yields a white solid G2. The molar ratio of p-hydroxybiphenyl to 1,6-dibromohexane is 1:2 to 1:3; the molar ratio of p-hydroxybiphenyl to K2CO3 is 1:2 to 1:4; and the molar ratio of p-hydroxybiphenyl to KI is 1:1 to 1:2.

[0021] The host-guest interaction between H2 and G2 was studied. To confirm whether strong interactions exist when H2 and G2 are mixed in organic solvents, we investigated host-guest complexation through a series of experiments. First, using... 1 Titration experiments of H2 and G2 were performed using 1H NMR spectroscopy. Figure 1 After the addition of G2, significant front-field shifts were observed in Ha-b and Hae of G2 due to the shielding effect of the cavity in the electron-rich columnar [5] aromatics. The results indicate that the alkyl chains on G2 penetrate the cavity of H2. The signal of the aromatic proton H3 of the columnar [5] aromatics shifted slightly downward due to the deshielding effect, which on the other hand proves that the alkyl chains on G2 spirally entered the cavity of H2. In addition, the H8-9 protons of H2 shifted forward, which may be due to the twisting and folding of H2 itself during the aggregation process.

[0022] II. Supramolecular polymers on Fe 3+ Research on recognition performance

[0023] At a concentration of 2.0 × 10 -5 15 equivalents of Fe were added to a solution of biphenylimidazolium-bridged bi-column[5] aromatic supramolecular polymer H2-G2 dimethyl sulfoxide. 3+ Cd 2+ Ag + Co 2+ Eu 3+ La 3+ Mg 2+ Cr 3+ Hg 2+ Ca 2+ 、Tb 3+ Al 3+ Ni 2+ Ba 2+ Zn 2+ Cu 2+ Pb 2+aqueous solution, the fluorescence signal of H2-G2 (DMSO / H2O, fw=18%, [c]= 2.0×10 -5 M) was found to be quenched when Fe -5 (1.0×10 3+ M) was added into the solution of H2-G2 (2.0×10 Figure 2 M) (as shown in Fig. 2a), and the color of fluorescence changed from blue to colorless (as shown in Fig. 2b) when the device was irradiated by 365 nm UV light. The addition of other cations did not change the fluorescence of H2-G2 solution. Figure 2

[0024] In addition, in order to further study the detection performance of H2-G2 for Fe 3+ , fluorescence titration experiment was carried out at room temperature, and it was found that the fluorescence intensity of H2-G2 gradually decreased (as shown in Fig. 3a) after the addition of Fe 3+ aqueous solution (1.0×10 -3 mol / L) into the solution of H2-G2. Linear fitting was carried out, and the lowest detection limit was 1.37×10 -5 mol / L (as shown in Fig. 3b). Figure 3 Figure 3

[0025] III. Portable Fe 3+ fluorescence detection device based on biphenyl bisimidazole bridged bis-p-quaterrylene supramolecular polymer

[0026] The portable Fe 3+ fluorescence detection device based on biphenyl bisimidazole bridged bis-p-quaterrylene supramolecular polymer comprises a UV lamp box body, a 365 nm UV lamp is fixed in the UV lamp box body, a sample chamber is detachably arranged at the bottom of the UV lamp box body, a cuvette is arranged in the sample chamber, a sample placing opening is arranged at the top end of the sample chamber, the cuvette is placed into the sample chamber through the sample placing opening, an entrance opening is arranged at the bottom of the 365 nm UV lamp, and the entrance opening is arranged directly above the sample placing opening; an observation opening is arranged at the front side of the sample chamber; and the device further comprises a smart phone, and the camera of the smart phone is directly opposite to the observation opening.

[0027] The UV lamp box body is made of light-proof material and is constructed by 3D printing. The sample chamber is made of black material which is light-proof and non-reflective. The UV lamp box body and the sample chamber are made of light-proof material, so that the device is in a darkroom state, and the influence of external environment on the detection result is effectively avoided.

[0028] Method for detecting Fe 3+ by using the Fe -5 fluorescence detection device

[0029] (1) Linear equation drawing: the UV lamp box body is detached from the sample chamber, 2 mL of H2-G2 solution with a concentration of 8×10​​​-5 mol / L biphenyl imidazole bridged bis-pyrene supermolecule polymer into a cuvette, then add a series of Fe 3+ standard solution, connect the UV lamp box to the top of the sample chamber, the UV lamp box and the sample chamber are in dark state, turn on the 365 nm UV lamp, take a photo through the observation port on the sample chamber by the smart phone, get the fluorescence photo, analyze the RGB value of the fluorescence photo by the smart phone APP "Color Picker", establish the standard linear equation of Fe 3+ concentration and RGB value;

[0030] Fe 3+ The concentration of the standard solution is 1.5×10 -5 mol / L ~ 1.5×10 -4 mol / L, the linear equation of Fe 3+ concentration and RGB value is y=-0.40x+114.09, R 2 ﹥0.99, wherein x is the concentration of Fe 3+ , unit: mol / L, y is the RGB value;

[0031] Fe 3+ The concentration of the standard solution is 1.5×10 -5 mol / L, 3×10 -5 mol / L, 4.5×10 -5 mol / L, 6×10 - 5 mol / L, 7.5×10 -5 mol / L, 9×10 -5 mol / L, 1.05×10 -4 mol / L, 1.2×10 -4 mol / L, 1.35×10 -4 mol / L, 1.5×10 -4 mol / L.

[0032] Color Picker mobile version is a very practical Android mobile phone color picking tool, which is very powerful, based on image color recognition technology, can easily extract local color of picture, manual adjustment of color picker, can easily view color related numerical information.

[0033] (2) Fe 3+ The determination of the sample to be tested

[0034] Take 2 mL of 8×10 -5 mol / L biphenyl imidazole bridged bis-pyrene supermolecule polymer into a cuvette, then add Fe 3+The solution to be tested was prepared by connecting the UV lamp housing to the sample chamber, creating a dark environment between the UV lamp housing and the sample chamber. The 365 nm UV lamp was then turned on, and a photograph was taken using a smartphone through the observation port on the sample chamber to obtain the Fe... 3+ The fluorescence image of the test solution was analyzed using the smartphone app "Color Picker," and the RGB values ​​were then substituted into the Fe... 3+ The standard linear equation for concentration and RGB values ​​yields Fe. 3+ Fe in the solution to be tested 3+ Concentration, to achieve Fe 3+ Quantitative detection.

[0035] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0036] This invention provides a method combining fluorescence detection technology and smartphone detection technology. It utilizes the smartphone's digital camera to capture colorimetric changes during fluorescence detection, converting them into RGB values ​​to establish a linear relationship between pollutant concentration and RGB values. This enables rapid and effective real-time quantitative analysis of pollutant concentrations on-site. The device is simple to operate, portable, minimally affected by environmental conditions, provides rapid detection, high timeliness, and has a wide range of applications, facilitating on-site detection and analysis. Attached Figure Description

[0037] Figure 1 Subject-guest titration for H2 and G2 1 H-NMR spectrum;

[0038] Figure 2 a) H2-G2 (2.0×10 -5 M) in DMSO / H 2 Fluorescence spectrum of O (fw, 18%) with cations (15 equivalents); b) Fe added under UV lamp 3+ Photos of H2-G2 before and after;

[0039] Figure 3 a) is Fe 3+ Fluorescent titration experiment of H2-G2; d) Fe at different concentrations 3+ Linear range of fluorescence spectrum after adding H2-G2;

[0040] Figure 4 For compound H2 1 H-NMR spectrum;

[0041] Figure 5 For compound H2 13 C-NMR spectrum;

[0042] Figure 6 For compound G2 1H-NMR spectrum;

[0043] Figure 7 Fe 3+ Structure diagram of fluorescence detection device;

[0044] Figure 8 Fe 3+ Structure diagram of fluorescence detection device;

[0045] In the figure: 1-365 nm ultraviolet lamp, 2-ultraviolet lamp box 2, 3-inlet, 4-cuvette, 5-sample inlet, 6-observation port, 7-sample chamber, 8-smartphone;

[0046] Figure 9 Physical map of detection device;

[0047] Figure 10 Effect image of detection device for detecting Fe 3+ ;

[0048] Figure 11 Linear relationship diagram of RGB mean value and Fe 3+ concentration measured by detection device. Specific implementation method

[0049] Example 1 Preparation of supramolecular polymer

[0050] Synthesis of biphenyl imidazole bridged double pillar [5] arene dimer:

[0051] (1) Dissolve p-methoxyphenol (3.72 g, 30 mmol) and K2CO3 (16 g, 120 mmol) in acetone, and dissolve KI (7.5 mmol, 1.2 g) and 1,4-dibromobutane (17.27 g, 80 mmol) in acetone, respectively, and reflux at 60 ℃ for 1 h, then mix the two in a 500 ml round-bottom flask, reflux at 65 ℃ for 48 h, cool to room temperature, and filter out the insoluble solid. Concentrate the filtrate to obtain the crude product, and purify it by column chromatography with petroleum ether: ethyl acetate = 20:1 as eluent to obtain the pure compound 1.

[0052] (2) Compound 1 (1.565 g, 5 mmol), 1,4-dimethoxybenzene (50 mmol) and 3.0 g of paraformaldehyde were dissolved in 200 mL of 1,2-dichloroethane, stirred at room temperature for 30 min, and then 6 mL of boron trifluoride etherate was added dropwise to the solution until the color of the solution was dark green, and the reaction was carried out at 30°C for 30 min. A large amount of water was added to quench the reaction, and the reaction was extracted with 1,2-dichloromethane three times, and then a small amount of anhydrous sodium sulfate was added to remove water. The insoluble solid was filtered, and the filtrate was concentrated to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane: ethyl acetate = 100:50:1 as the eluent to obtain pure compound 2.

[0053] (3) Compound 2 (1.7406 g, 2.0 mmol), 3 (0.3542 g, 3.0 mmol), KI (0.083 g, 0.5 mmol) and KOH (0.18 g, 4.5 mmol) were added to DMF (80 mL) and refluxed at 65°C for 48 hours. After cooling to room temperature, the insoluble solid was filtered, and the filtrate was concentrated to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane: methanol = 100:50:1 as the eluent to obtain pure H1, a white solid (0.91 g, 46%), m.p. = 104-106°C.

[0054] (4) Compound H1 (0.1 g, 0.11 mmol) and Cu(OAc)2 (0.0264 g, 0.145 mmol) were added to xylene (10 mL). The solution was refluxed at 140°C for 12 hours. After cooling to room temperature, the insoluble solid was filtered. The filtrate was concentrated to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: ethyl acetate = 3:1 as the eluent to obtain pure H2, a white solid (0.0508 g, 50.8%), m.p. = 192-194°C. The H-NMR spectrum and the C-NMR spectrum of H2 are shown in FIGS. 1 and 2, respectively. 1 H-NMR spectrum and 13 C-NMR spectrum as Figure 4 、 Figure 5 .

[0055] The synthesis route is as follows:

[0056]

[0057] Synthesis of guest molecule G2:

[0058] Para-hydroxybiphenyl (2.1 g, 20.0 mmol), K2CO3(8.4 g, 60 mmol), KI (3.3 g, 20 mmol), 1,6-dibromohexane (12.2 g, 50 mmol) and acetone (400.0 mL) were added into a 500 mL round-bottom flask. The reaction mixture was stirred at reflux under nitrogen atmosphere at 65 °C for 48 h. After filtration of the solid, the solvent was evaporated and the residue was dissolved in CH2Cl2. Column chromatography (silica gel; petroleum ether: ethyl acetate = 20:1) gave a white solid (6.54 g, 75%). G2 1 H-NMR spectrum is shown in Figure 1. Figure 7 .

[0059] The synthetic route is as follows:

[0060]

[0061] Preparation of biphenylimidazole-bridged bis-porphyrin[5]arene supramolecular polymer:

[0062] Firstly, 1.0 x 10 -3 mol / L biphenylimidazole-bridged bis-porphyrin H2 solution was prepared with dimethyl sulfoxide; then, 1.0 x 10 -3 mol / L G2 solution was prepared with dimethyl sulfoxide; finally, 2 mL of 1.0 x 10 -3 mol / L H2 solution and 2 mL of 1.0 x 10 -3 mol / L G2 solution were mixed in 96 mL of DMSO, and a biphenylimidazole-bridged bis-porphyrin[5]arene supramolecular polymer H2-G2 with a concentration of 2.0 x 10 - 5 mol / L was self-assembled at room temperature.

[0063] Example 2 Recognition of Fe 3+

[0064] In the dimethyl sulfoxide solution of biphenylimidazole-bridged bis-porphyrin[5]arene supramolecular polymer with a concentration of 2.0 x 10 -5 mol / L, 15 equivalent of Fe 3+ , Cd 2+ , Ag + , Co 2+ , Eu 3+ , La 3+ , Mg 2+ , Cr 3+ , Hg 2+ , Ca 2+ , Tb 3+ , Al3+ , Ni 2+ , Ba 2+ , Zn 2+ , Cu 2+ , Pb 2+ , if the fluorescence of the supramolecular polymer is quenched or the fluorescence color of the supramolecular polymer solution changes from blue to colorless under the irradiation of a 365 nm ultraviolet lamp, it indicates that Fe 3+ is added; if the fluorescence of the supramolecular polymer does not change, it indicates that Fe 3+ is not added.

[0065] Example 3 Fe 3+ fluorescence detection device and detection method

[0066] As shown in Figures 7-8 , the portable Fe 3+ fluorescence detection device based on the biphenyl imidazole bridged double pillar [5] arene supramolecular polymer includes an ultraviolet lamp box body 2, a 365 nm ultraviolet lamp 1 is fixed in the ultraviolet lamp box body 2, a sample chamber 7 is detachably arranged at the bottom of the ultraviolet lamp box body 1, a cuvette 4 is arranged in the sample chamber 7, a sample opening 5 is arranged at the top end of the sample chamber 7, the cuvette 4 is placed into the sample chamber 7 through the sample opening 5, an entrance light opening 3 is arranged at the bottom of the 365 nm ultraviolet lamp 1, and the entrance light opening 3 is arranged directly above the sample opening 5; an observation opening 6 is arranged at the front side of the sample chamber 7; the fluorescence detection device further includes a smart phone 8, and the camera of the smart phone 8 is directly opposite the observation opening 6.

[0067] The ultraviolet lamp box body 2 is made of light-proof material and is constructed by using 3D printing. The sample chamber 7 is made of black material which is light-proof and non-reflective. The ultraviolet lamp box body 2 and the sample chamber 7 are made of light-proof material, so that the device is in a darkroom state, effectively avoiding the influence of the external environment on the detection result.

[0068] Fe 3+ fluorescence detection device and detection method 3+

[0069] (1) Linear equation drawing: the ultraviolet lamp box body is detached from the sample chamber, 2 mL of biphenyl imidazole bridged double pillar [5] arene supramolecular polymer with a concentration of 8 × 10 -5 mol / L is placed in the cuvette 6, and a Fe 3+ standard solution is added, the ultraviolet lamp box body is connected to the top of the sample chamber, the ultraviolet lamp box body and the sample chamber 7 are in a darkroom state, the 365 nm ultraviolet lamp is turned on, and the smart phone 8 is used to take a photo through the observation opening 6 on the sample chamber 7, so as to obtain a fluorescence photo, and the RGB value (generally the average RGB value) of the fluorescence photo is analyzed by using the smart phone APP “Color Picker”, and a standard linear equation of the Fe 3+ concentration and the RGB value is established. Figure 11 ​);

[0070] Fe 3+ concentration in the range of 1.5×10 -5 mol / L ~ 1.5×10 -4 mol / L, the linear equation of Fe 3+ concentration and RGB value is y=-0.40x+114.09, R 2 >0.99, wherein x is the Fe 3+ concentration, unit: mol / L, y is the RGB value;

[0071] Fe 3+ standard solution with a concentration of 1.5×10 -5 mol / L, 3×10 -5 mol / L, 4.5×10 -5 mol / L, 6×10 - 5 mol / L, 7.5×10 -5 mol / L, 9×10 -5 mol / L, 1.05×10 -4 mol / L, 1.2×10 -4 mol / L, 1.35×10 -4 mol / L, 1.5×10 -4 mol / L.

[0072] (2) Fe 3+ determination of the sample to be tested

[0073] Take 2 mL of biphenyl imidazole bridged double column [5] arene supramolecular polymer with a concentration of 8×10 -5 mol / L and put it into cuvette 6, then add Fe 3+ solution to be tested, connect the ultraviolet lamp box 2 to the top of the sample chamber 7, and the ultraviolet lamp box 2 and the sample chamber 7 are in dark state, turn on the 365 nm ultraviolet lamp 1, take a photo through the observation port 6 on the sample chamber 7 by the smart phone 8, and get the fluorescence photo of Fe 3+ solution to be tested, the fluorescence photo is analyzed by the RGB value of the smart phone APP "Color Picker", and the RGB value is substituted into the standard linear equation of Fe 3+ concentration and RGB value, and the Fe 3+ concentration in the sample to be tested is calculated. 3+ concentration, and the concentration of Fe 3+ is quickly and effectively realized in real-time quantitative on-site analysis.

[0074] In order to verify the fluorescence detection effect of the detection device, the device is used to take photos of Fe 3+The fluorescence effect of the solution (c = 130 μM) is shown in the following figure Figure 10 The mean value of the RGB value is 56, which is calculated by the software ColorPicker on the smart phone. The linear equation is used to calculate the Fe 3+ The solution concentration is 136 μM, which can ensure accuracy, and the use of the device for shooting can reduce the influence of the external environment on the smart phone results, effectively realizing the observation and shooting of the sample.

Claims

1. A biphenyl imidazole bridged bis-porphyrin supramolecular polymer, which is formed by self-assembly of biphenyl imidazole bridged bis-porphyrin dimer as host and 1, 4-bis (6-bromohexyloxy) benzene as guest in dimethyl sulfoxide solution; The structural formula of biphenyl imidazole bridged bis-porphyrin dimer is: The structural formula of 1, 4-bis (6-bromohexyloxy) benzene is: 。 2. A method for preparing the biphenyl imidazole bridged bis- pillar[5]arene supramolecular polymer according to claim 1, characterized by: The biphenyl imidazole bridged bis-porphyrin supramolecular polymer is formed by self-assembly of the biphenyl imidazole bridged bis-porphyrin dimer and 1, 4-bis (6-bromohexyloxy) benzene in dimethyl sulfoxide solution at room temperature, and the molar ratio of the biphenyl imidazole bridged bis-porphyrin dimer to 1, 4-bis (6-bromohexyloxy) benzene is 1:

1.

3. The bipyrrolo[2,3-b]pyrido[3,4-d]imidazole bridged bis-porphyrin [5]arene supramolecular polymer of claim 1, characterized in that: The preparation method of the biphenyl imidazole bridged bis-porphyrin dimer comprises the following steps: (1) p-methoxyphenol and K2CO3 are dissolved in acetone, KI and 1, 4-dibromobutane are dissolved in acetone, and then refluxed at 60-70 ℃ for 1-2 h, and then mixed, and refluxed at 60-70 ℃ for 45-50 h, and then cooled to room temperature, filtered, and the filtrate was concentrated to obtain a crude product, which was purified by column chromatography to obtain 1-(4-bromobutoxy)-4-methoxybenzene; (2) 1-(4-bromobutoxy)-4-methoxybenzene, 1, 4-dimethoxybenzene and paraformaldehyde are dissolved in 1, 2-dichloroethane, stirred at room temperature, and then trifluoroboron ether is added dropwise until the solution color is dark green, and then reacted at 25-35 ℃ for 30 min, and then quenched by adding water, extracted with 1, 2-dichloromethane, and then dehydrated with anhydrous sulfuric acid, filtered to remove insoluble solids, and the filtrate was concentrated to obtain a crude product, which was purified by column chromatography to obtain a single modified column [5] arene; (3) the single modified column [5] arene, benzimidazole, KI and KOH are added to DMF, and refluxed at 60-70 ℃ for 45-50 h, and then cooled to room temperature, filtered, and the filtrate was concentrated to obtain a crude product, which was purified by column chromatography to obtain a benzimidazole functionalized column [5] arene; (4) the benzimidazole functionalized column [5] arene and Cu(OAc)2 are added to xylene, and refluxed at 130-150 ℃ for 10-15 h, and then cooled to room temperature, filtered, and the filtrate was concentrated to obtain a crude product, which was purified by column chromatography to obtain biphenyl imidazole bridged bis-porphyrin dimer.

4. The bipyrrolo[2,3-b]pyrido[3,4-d]bis[5]helicene supermolecule polymer of claim 3, wherein: The molar ratio of p-methoxyphenol to 1,4-dibromobutane in step (1) is 1:2-1:3; the molar ratio of p-methoxyphenol to K2CO3 is 1:3-1:5; the molar ratio of KI to 1,4-dibromobutane is 1:10-1:12; in step (2), the molar ratio of 1-(4-bromobutoxy)-4-methoxybenzene to 1,4-dimethoxybenzene is 1:10-1:12; the mass ratio of 1-(4-bromobutoxy)-4-methoxybenzene to paraformaldehyde is 1:1-1:2; in step (3), the molar ratio of single-modified column [5] arene to benzimidazole is 1:1-1:2; the molar ratio of single-modified column [5] arene to KI is 1:0.2-1:0.3; the molar ratio of single-modified column [5] arene to KOH is 1:2-1:3; in step (4), the molar ratio of benzimidazole functionalized column [5] arene to Cu(OAc)2 is 1:1-1:

2.

5. The bipyrrolo[2,3-b]pyrido[3,4-d]bis[5]hemicryptophane supramolecular polymer of claim 1, wherein: The preparation method of 1,4-bis(6-bromohexyloxy)benzene is as follows: p-hydroxydiphenyl, K2CO3, KI and 1,6-dibromohexane are added into acetone, the reaction mixture is stirred at 60-70 DEG C under nitrogen atmosphere for 45-50 h, the solid is filtered out, the solvent is evaporated and the residue is dissolved in CH2Cl2, and column chromatography is performed to obtain white solid 1,4-bis(6-bromohexyloxy)benzene.

6. The bipyrrolo[2,3-b]pyrido[3,4-d]bis[5]helicene supermolecule polymer of claim 5, wherein: The molar ratio of p-hydroxydiphenyl to 1,6-dibromohexane is 1:2-1:3; the molar ratio of p-hydroxydiphenyl to K2CO3 is 1:2-1:4; the molar ratio of p-hydroxydiphenyl to KI is 1:1-1:

2.

7. The application of the biphenyl imidazole bridged bis-quadricyclene [5] arene supramolecular polymer of claim 1 in fluorescent detection of Fe 3+ .

8. The application of the biphenyl imidazole bridged bis-porphyrin [5] arene supramolecular polymer in fluorescent detection of Fe 3+ characterized in that: In the solution of the biphenyl imidazole bridged bis-p-quaterrylene supramolecular polymer in dichloro sulfide, the addition of Fe 3+ , Cd 2+ , Ag + , Co 2+ , Eu 3+ , La 3+ , Mg 2+ , Cr 3+ , Hg 2+ , Ca 2+ , Tb 3+ , Al 3+ , Ni 2+ , Ba 2+ , Zn 2+ , Cu 2+ , Pb 2+ aqueous solution, only the addition of Fe 3+ can make the fluorescence of the supramolecular polymer quenched, and under the irradiation of 365 nm ultraviolet lamp, the fluorescence color of the supramolecular polymer solution changes from blue to colorless.

9. A portable Fe-based bis(biphenyl imidazole)-bridged bisqubit[5]arene supramolecular polymer of claim 1. 3+ A fluorescence detection device characterized by: The ultraviolet lamp box (2) is detachably provided with a sample chamber (7) at the bottom, the sample chamber (7) is provided with a cuvette (4), and the top end of the sample chamber (7) is provided with a sample placing opening (5), the cuvette (4) is placed into the sample chamber (7) through the sample placing opening (5), the bottom of the 365 nm ultraviolet lamp (1) is provided with a light inlet (3), and the light inlet (3) is arranged directly above the sample placing opening (5); the front side of the sample chamber (7) is provided with an observation opening (6); the fluorescence detection device further comprises a smart phone (8), and the camera of the smart phone (8) is directly opposite the observation opening (6); the ultraviolet lamp box (2) and the sample chamber (7) are made of light-proof materials.

10. The portable Fe of claim 9, wherein the Fe is configured to be worn on a user's body. 3+ A fluorescence detection device characterized by: The fluorescence detection device detects Fe 3+ in the following steps: Linear equation drawing: the UV lamp box was detached from the sample chamber, and the 8 x 10 -5 mol / L biphenyl imidazole bridged double column [5] arene supramolecular polymer was taken out and placed in a cuvette, then a series of Fe 3+ standard solutions were added, the UV lamp box was connected to the top of the sample chamber, the UV lamp box and the sample chamber were in a dark room state, a 365 nm UV lamp was turned on, and a smartphone was used to take a photo through the observation port on the sample chamber to obtain a fluorescence photo. The fluorescence photo was analyzed by the RGB value through the smartphone APP "Color Picker", and a standard linear equation of Fe 3+ concentration and RGB value was established; Fe 3+ concentrations of 1.5 x 10 -5 mol / L ~ 1.5 x 10 -4 mol / L, the linear equation of Fe 3+ concentration and RGB value is y = -0.40x + 114.09, R 2 > 0.99, where x is the Fe 3+ concentration, unit: mol / L, y is the RGB value. Fe 3+ The concentration of the standard solution is 1.5 x 10 -5 mol / L, 3 x 10 -5 mol / L, 4.5 x 10 -5 mol / L, 6 x 10 -5 mol / L, 7.5 x 10 -5 mol / L, 9 x 10 -5 mol / L, 1.05 x 10 -4 mol / L, 1.2 x 10 -4 mol / L, 1.35 x 10 -4 mol / L, 1.5 x 10 -4 mol / L; Fe 3+ Determination of the sample to be tested Take the concentration of 8 x 10 -5 mol / L biphenyl imidazole bridged double column [5] arene supramolecular polymer into the cuvette, then add Fe 3+ The test solution, the ultraviolet lamp box is connected to the sample chamber above, the ultraviolet lamp box and the sample chamber are dark state, open 365 nm ultraviolet lamp, through the observation port on the sample chamber of smart phone to take pictures, get Fe 3+ The fluorescence photo of the test solution, the fluorescence photo is analyzed by smart phone APP "Color Picker", and the RGB value is substituted into Fe 3+ The standard linear equation of concentration and RGB value, the concentration of Fe 3+ The concentration of Fe 3+ In the test solution, the concentration of Fe 3+ Real-time quantitative detection of the concentration of Fe.

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