Environmental humidity response type circular polarization luminescence supramolecular polymer as well as preparation method and application thereof

Abstract

The invention discloses an environment humidity response type circular polarization luminescence supramolecular polymer and a preparation method and application thereof.The preparation method comprises the steps that HYQUICC is dissolved in an organic solvent dimethyl sulfoxide, ultrasonic induction self-assembly is conducted after heating dissolution, and the supramolecular polymer with cyan fluorescence is formed; through the synergistic effect of an excited-state intramolecular proton transfer mechanism and a supramolecular dynamic self-assembly characteristic, humidity-driven fluorescence color change and CPL signal inversion are realized. Meanwhile, the CPL signal is switched from the negative direction to the positive direction, and the response time is obviously shortened along with the rising of the humidity. The material has high sensitivity (wide humidity response range and adjustable signal linearity), multi-dimensional optical output (intensity, wavelength and polarization state) and excellent stability (self-repairing characteristic), and overcomes the defects that a traditional fluorescence sensor is susceptible to interference and single in signal.

Description

TECHNICAL FIELD

[0001] The present application relates to functional polymer materials and preparation methods, in particular to an environmental humidity responsive circularly polarized luminescence supramolecular polymer and a preparation method thereof. BACKGROUND

[0002] Humidity, as a key physical quantity representing the water vapor content in the environment, is directly related to the precise regulation of industrial production (such as semiconductor packaging, drug storage), agricultural ecology (such as greenhouse regulation, soil moisture monitoring), medical health (such as respiratory monitoring, sterile environment control), weather prediction, and energy management (such as lithium battery electrolyte environment control). Traditional humidity detection mainly relies on resistance or capacitance sensors, which realize humidity sensing through the change of electrical properties after the material absorbs moisture, but it is susceptible to electromagnetic interference, response lag, and difficult to achieve spatial resolution measurement. In recent years, fluorescent humidity sensing materials have developed rapidly due to their visual optical signal, anti-electromagnetic interference, and high sensitivity. For example, humidity probes based on fluorescence intensity changes or wavelength shifts have been widely studied. However, such materials still have significant defects: 1) the fluorescence signal is easily affected by light bleaching, ion interference, or temperature fluctuations, resulting in insufficient long-term stability; 2) single-dimensional optical signals (such as intensity or wavelength) are difficult to realize multi-parameter joint analysis, limiting the reliability in complex scenarios.

[0003] Circularly polarized luminescence (CPL) materials emit circularly polarized light with chiral characteristics, providing intensity, wavelength, and polarization state (left-handed / right-handed) triple optical signals, bringing multi-dimensional information and anti-interference advantages to humidity detection. Further constructing CPL supramolecular polymer materials, using dynamic non-covalent bonds (such as hydrogen bonds, host-guest recognition, and electrostatic interactions) to drive self-assembly, makes the material have structure programmability, stimulus responsiveness, and self-repairing ability, which is particularly suitable for constructing CPL responsive humidity sensing materials: the reversibility of non-covalent bonds allows the material to trigger assembly changes or disassembly through humidity changes, realizing the switching of CPL signals; at the same time, supramolecular polymers can amplify CPL, making it easy to monitor humidity-sensitive CPL. Therefore, it is of considerable practical significance and application prospect to invent a simple, low-cost, high-sensitivity, and anti-interference CPL supramolecular polymer humidity detection material. SUMMARY

[0004] The purpose of the present application is to provide an environmental humidity responsive CPL supramolecular polymer and a preparation method thereof, an environmental humidity responsive circularly polarized luminescence supramolecular polymer and a preparation method thereof. The material combines the dynamic reversible characteristics of supramolecular polymers and the circularly polarized luminescence function, and realizes the structural sensitivity and optical responsiveness of the material in the environmental humidity environment through molecular design.

[0005] The material takes cholesteric derivative HYQUICC as a functional unit, cooperates with supramolecular dynamic self-assembly characteristics through excited state intramolecular proton transfer (ESIPT) mechanism, realizes humidity-driven fluorescence color change and CPL signal inversion. The preparation method comprises the following steps: dissolving HYQUICC in super-dry dimethyl sulfoxide (DMSO), ultrasonic self-assembly after heating and dissolving, forming a supramolecular polymer with cyan fluorescence; by regulating the environmental humidity (18% to 88%), the fluorescence of the material is quickly changed from cyan to blue, and the CPL signal is switched from negative to positive, and the response time is significantly shortened as the humidity increases. The material has high sensitivity (wide humidity response range, linear adjustable signal), multi-dimensional optical output (intensity, wavelength, polarization state) and excellent stability (self-repairing characteristics), and overcomes the defects that the traditional fluorescent sensor is easy to be disturbed and the signal is single. Its preparation process is simple, low in cost, and can be applied to environmental humidity monitoring, optical information encryption and intelligent sensor device development.

[0006] Technical scheme: the preparation method of the environmental humidity response type circularly polarized luminescence supramolecular polymer, dissolving HYQUICC in super-dry dimethyl sulfoxide DMSO, ultrasonic self-assembly after heating and dissolving, forming a supramolecular polymer with cyan fluorescence,

[0007] Among them, the structure of HYQUICC is as follows:

[0008]

[0009] The CPL supramolecular polymer material provided by the application is formed by HYQUICC in super-dry organic solvent dimethyl sulfoxide.

[0010] Further, in the supramolecular polymer, the molar concentration of HYQUICC in DMSO is 10-30 mM, preferably 16 mM.

[0011] Further, the heating temperature is 80-120 DEG C, preferably 100 DEG C.

[0012] Further, the power of the ultrasonic cleaner is 120-150 W.

[0013] Further, the preparation method of the HYQUICC is as follows,

[0014] The synthesis route of HYQUICC is as follows:

[0015]

[0016] The specific synthesis steps are as follows:

[0017] a) ethylenediamine is dissolved in dry dichloromethane, then cholesteryl formyl chloride is dissolved in dry dichloromethane, added dropwise into ethylenediamine, stirred, left to stand, extracted with saturated brine and DCM to obtain a light yellow oily product;

[0018] b) the oily product is dissolved in tetrahydrofuran, BOP reagent, triethylamine, 8-hydroxyquinoline-7-carboxylic acid are added, reacted, the crude product is purified to obtain a white powder product.

[0019] Further, the molar mass ratio of ethylenediamine and cholesteryl formyl chloride in the a) is 1.5:1-1:1, preferably 1:1.

[0020] Further, the molar mass ratio of BOP reagent, triethylamine and 8-hydroxyquinoline-7-carboxylic acid in the b) is 1.5-1:1.5-1:1-1, preferably 1:1:1.

[0021] Further, the formation of the CPL supramolecular polymer is confirmed by a circular dichroism spectrometer, a circular polarization spectrometer, a fluorescence spectrometer, a scanning electron microscope and the like.

[0022] The application of the supramolecular polymer in humidity response.

[0023] The application provides a preferred method for preparing the CPL supramolecular polymer material with environmental humidity response, comprising the following steps:

[0024] 1) HYQUICC compound is dispersed in a glass sample bottle containing solvent super-dry dimethyl sulfoxide, heated to 100 DEG C until the solution is clear, then placed in an ultrasonic cleaner at room temperature until the solution becomes turbid (30-60s), and a flocculent precipitate is visible to the naked eye, to obtain a CPL supramolecular polymer material emitting cyan fluorescence;

[0025] 2) the CPL supramolecular polymer material emitting cyan fluorescence in step 1 is applied on a 0.1mm colorimetric cell clamp, then placed in airtight containers with relative humidity of 18%, 32%, 47%, 65% and 88% respectively, and the change in fluorescence emission over time is observed.

[0026] Compared with the prior art, the application has the following beneficial effects:

[0027] 1) The CPL supramolecular polymer material is prepared by heating-ultrasonic method in super-dry dimethyl sulfoxide solvent using cholesteryl derivative HYQUICC;

[0028] 2) HYQUICC has an excited state intramolecular proton transfer (ESIPT) site, exhibits fluorescence response to water and humidity and inversion of circularly polarized luminescence signal, and can be used for sensing humidity, thus having certain application prospect.

[0029] 3. The technology relates to materials with high sensitivity, higher security, stability, low cost, visualization, easy operation and recyclability. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 Hydrogen spectrum for characterizing the nuclear magnetic structure of HYQUICC described in the specific embodiment;

[0031] Figure 2 Carbon spectrum for characterizing the nuclear magnetic structure of HYQUICC described in the specific embodiment;

[0032] Figure 3 Mass spectrum for characterizing the HYQUICC described in the specific embodiment;

[0033] Figure 4 Macroscopic and fluorescence photographs of CPL supramolecular polymer formed by HYQUICC in super dry dimethyl sulfoxide described in the specific embodiment;

[0034] Figure 5 Scanning electron micrograph of CPL supramolecular polymer formed by HYQUICC in super dry dimethyl sulfoxide described in the specific embodiment;

[0035] Figure 6 Fluorescence change process of CPL supramolecular polymer prepared by HYQUICC in super dry dimethyl sulfoxide for humidity response in the specific embodiment;

[0036] Figure 7 Fluorescence spectrum monitoring process chart of CPL supramolecular polymer prepared by HYQUICC in super dry dimethyl sulfoxide at a relative humidity of 18% in the specific embodiment;

[0037] Figure 8 Circularly polarized luminescence spectrum of CPL supramolecular polymer prepared by HYQUICC in super dry dimethyl sulfoxide at a relative humidity of 18% in the specific embodiment. DETAILED DESCRIPTION

[0038] In order to make the purpose, technical scheme and advantages of the present application clearer, the technical scheme of the present application will be further described below.

[0039] Preparation method of cholesteric derivative HYQUICC in Example 1

[0040] The synthesis route of HYQUICC is as follows:

[0041]

[0042] Specific synthesis steps of HYQUICC:

[0043] a) Ethylenediamine (3.81 g, 62.3 mmol) was dissolved in an appropriate amount of dry dichloromethane and placed at 0-5 °C, then cholesteryl carbonyl chloride (2 g, 4.45 mmol) was dissolved in dry dichloromethane and then added dropwise to the ethylenediamine under vigorous stirring, after the addition was completed, it was transferred to room temperature and stirred overnight. Then the reaction solution was extracted with saturated brine (100 mL x 3) and DCM for 3 times, the organic layer was dried over anhydrous magnesium sulfate and rotary evaporated to obtain a light yellow oily product;

[0044] b) The product of the previous step was dissolved in tetrahydrofuran without purification, 1 equivalent of BOP reagent, 1 equivalent of triethylamine, 1 equivalent of 8-hydroxyquinoline-7-carboxylic acid were added, and refluxed for 3 h. After the reaction solution was cooled to room temperature, the solvent was removed under reduced pressure, the residue was dissolved in chloroform and washed with saturated brine three times, the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The crude product was purified by column chromatography in DCM / MeOH = 20 / 1. The white powder product was obtained with a yield of 60%.

[0045] The structure characterization data of HYQUICC are as follows:

[0046] 1 H NMR (400 MHz, Chloroform-d) δ 8.92 (dd, J = 4.3, 1.6 Hz, 1H), 8.22 (m, 2H), 8.07 (d, J = 8.8 Hz, 1H), 7.57 (dd, J = 8.3, 4.3 Hz, 1H), 7.38 (d, J = 8.9 Hz, 1H), 5.33 (d, J = 4.9 Hz, 1H), 5.28 (s, 1H), 4.53 (dt, J = 11.6, 6.5 Hz, 1H), 3.68 (t, J = 5.6 Hz, 2H), 3.52 (d, J = 6.0 Hz, 2H), 2.32 (dt, J = 17.9, 12.2 Hz, 2H), 2.02 (dt, J = 12.5, 3.4 Hz, 1H), 1.85 (m, 3H), 1.45 (m, 14H), 1.14 (dd, J = 9.2, 5.4 Hz, 4H), 1.09 (d, J = 3.4 Hz, 1H), 1.00 (s, 4H), 0.93 (d, J = 6.5 Hz, 4H), 0.88 (dd, J = 6.6, 1.9 Hz, 7H), 0.69 (s, 3H).

[0047] 13C NMR (151 MHz, CDCI3) δ 167.82, 157.46, 149.10, 140.14, 139.27, 136.36, 130.70, 126.67, 123.70, 122.82, 117.93, 113.32, 75.03, 68.33, 57.04, 56.48, 50.34, 42.65, 41.20, 41.14, 40.08, 39.87, 38.82, 37.30, 36.88, 36.53, 36.14, 32.24, 32.19, 28.58, 28.42, 28.36, 24.63, 24.18, 23.17, 22.91, 21.37, 19.65, 19.06, 12.20.

[0048] HRMS (MALDI-TOF): m / z calcd for C 40 H57N3O4[M] + : 642.4349, found: 642.4528.

[0049] Example 2 Preparation of HYQUICC circularly polarized luminescent supramolecular polymer

[0050] Take a clean sample bottle, weigh 3 mg of HYQUICC (16 mmol) as an organic small molecule, and use a pipette to add 300 μL of ultradry dimethyl sulfoxide solvent to the sample bottle. Then place it in a 100 °C oven until it is clear, and then immediately place it in an ultrasonic cleaner at room temperature for ultrasonic treatment until flocculent precipitate appears in the bottle. The HYQUICC circularly polarized luminescent supramolecular polymer material is obtained, which exhibits greenish blue fluorescence emission. The macroscopic photograph, scanning electron microscope image, circularly polarized luminescence spectrum, and fluorescence spectrum of the material are shown in Figs. 2, 3, 4, and 5, respectively. Figure 4

[0051] Example 3 Environmental humidity sensing process of HYQUICC circularly polarized luminescent supramolecular polymer

[0052] Take the HYQUICC circularly polarized luminescent supramolecular polymer material described in Example 2, and place it in a sealed container with a relative humidity of 18%, 32%, 47%, 65%, and 88%, respectively, and observe the change in fluorescence emission over time, as shown in Fig. 6. As the humidity increases, the speed at which the circularly polarized luminescence changes from greenish blue to blue becomes faster and faster (Fig. 7), the response time becomes shorter and shorter, and at the same time the circularly polarized luminescence signal is reversed from negative to positive (Fig. 8). Figure 6 Figure 7 Figure 8

[0053] The power of the ultrasonic cleaner is 150 W. ​​​​

[0054] The above merely describes the preferred embodiments of the present application and does not limit the present application in any way. Any person skilled in the art can make any form of equivalent replacement, modification or change to the technical solutions and technical contents disclosed by the present application without departing from the scope of the technical solutions of the present application, and such still falls within the protection scope of the present application.

Claims

1. A method for preparing an environmental humidity-responsive circularly polarized luminescent supramolecular polymer, characterized in that, HYQUICC was dissolved in the organic solvent dimethyl sulfoxide (DMSO), and after heating and dissolution, it underwent ultrasonic-induced self-assembly to form a supramolecular polymer with cyan fluorescence. The HYQUICC structure is as follows:

2. The method for preparing the environmental humidity-responsive circularly polarized luminescent supramolecular polymer according to claim 1, characterized in that, In the supramolecular polymer product, the molar concentration of HYQUICC is 10-30 mM, preferably 16 mM.

3. The method for preparing the environmental humidity-responsive circularly polarized luminescent supramolecular polymer according to claim 1, characterized in that, The heating temperature is 80-120℃, preferably 100℃.

4. The method for preparing the environmental humidity-responsive circularly polarized luminescent supramolecular polymer according to claim 1, characterized in that, The power of the ultrasonic cleaner is 120-150W.

5. The method for preparing the environmental humidity-responsive circularly polarized luminescent supramolecular polymer according to claim 1, characterized in that, The preparation method of the HYQUICC is as follows: The synthesis route for HYQUICC is as follows: Specific synthesis steps: a) Ethylenediamine was dissolved in dry dichloromethane, and then cholesterol formyl chloride was dissolved in dry dichloromethane and added dropwise to ethylenediamine. The mixture was stirred, allowed to stand, and extracted with saturated brine and DCM to obtain a light yellow oily product. b) The oily product was dissolved in tetrahydrofuran, and BOP reagent, triethylamine, and 8-hydroxyquinoline-7-carboxylic acid were added. The reaction was carried out, and the crude product was purified to obtain a white powder product.

6. The method for preparing the environmental humidity-responsive circularly polarized luminescent supramolecular polymer according to claim 1, characterized in that, The molar mass ratio of ethylenediamine and cholesterol formyl chloride in a) is 1.5:1 to 1:1, preferably 1:

1.

7. The method for preparing the environmental humidity-responsive circularly polarized luminescent supramolecular polymer according to claim 1, characterized in that, In b), the molar ratio of BOP reagent, triethylamine, and 8-hydroxyquinoline-7-carboxylic acid is 1.5-1:1.5-1:1-1, preferably 1:1:

1.

8. The application of the supramolecular polymer prepared by the method according to any one of claims 1-4 in humidity response.

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