Supramolecular hydrogel based on decamethyl cucurbit [5] uril as well as preparation method and application of supramolecular hydrogel

Abstract

The invention belongs to the technical field of supramolecular hydrogel preparation, and particularly relates to a decamethyl cucurbit [5] uril-based supramolecular hydrogel and a preparation method and application thereof.The decamethyl cucurbit [5] uril-based supramolecular hydrogel is prepared from decamethyl cucurbit [5] uril and 2, 2 '-diamino-1, 1'-binaphthalene hydrochloride, the synthesis method is simple in step, low in synthesis cost and green in synthesis process, decamethyl cucurbit [5] uril is used as a main solution, 2, 2 '-diamino-1, 1'-binaphthalene hydrochloride is used as a guest solution, the possibility of fluorescence aggregation quenching is reduced by adding ethanol, and after the fluorescent dye sulfonyl rhodamine B is introduced, the fluorescence intensity of the fluorescent dye is greatly improved. According to the present invention, the Cucurbit [10]-decamethyl [5] cucurbit [10] uril and the 2, 2 '-diamino-1, 1'-binaphthalene hydrochloride compound can be adopted as the receptor of fluorescence resonance energy transfer, and the chiral transfer of the Cucurbit [10]-decamethyl [5] uril and the 2, 2 '-diamino-1, 1'-binaphthalene hydrochloride compound can be achieved in the hydrogel system so as to produce the adjustable emission color, such that the preparation of the white light circular polarization

Description

Technical Field

[0001] The invention belongs to the technical field of supramolecular hydrogel preparation, and in particular relates to a supramolecular hydrogel based on decamethyl five-membered cucurbitacin and a preparation method and application thereof. Background Art

[0002] Circularly polarized luminescent (CPL) materials have become a research hotspot in the past decade due to their unique optical properties and great application potential in optical devices, sensors and imaging technology. Decamethyl five-membered cucurbitacin is a macrocyclic host molecule with a special cavity structure, which is expected to be co-assembled with guest molecules to form CPL materials. The main preparation methods include: metal ion coordination, chiral template method, non-chiral conjugated polymer doped with chiral inducers, etc. However, due to the irregular movement in the solution and the influence of quenching factors such as oxygen, the fluorescence emission will be limited, thereby affecting the luminescence efficiency and luminescence stability of circularly polarized luminescent materials, and hydrogels are not widely used in the preparation of CPL materials. Existing white CPL gel materials often need to undergo complex organic synthesis steps to connect the chiral source and the luminophore by covalent bonds.

[0003] Although the invention patent with publication number CN111410953A discloses a circularly polarized luminescent supramolecular gel and its preparation method and application, with C2 symmetrical phenylalanine derivatives as chiral gel factors, condensed aromatic hydrocarbons or benzene condensed heterocyclic compounds as non-chiral fluorescent molecules, the chiral gel factors and non-chiral fluorescent molecules are co-assembled through intermolecular hydrogen bonds and π-π interactions to obtain a circularly polarized luminescent supramolecular hydrogel, but this method uses acetonitrile solvent, which is more toxic and expensive than water, and it does not use cucurbituril as the main molecule. Although the invention patent with publication number CN118405967A mentions that circularly polarized luminescent materials can be prepared for classical supramolecular macrocyclic main molecules such as pillar aromatic hydrocarbons, calix aromatic hydrocarbons and cucurbituril, it does not specifically disclose a method for producing circularly polarized luminescent gel using cucurbituril as a raw material.

[0004] In existing CPL materials, luminescent materials containing chiral molecules are usually used, such as chiral ligands and macrocyclic compounds for co-assembly, so as to achieve circularly polarized luminescence through chirality transfer. However, this type of material has not made significant progress in the construction of white light CPL, and the color controllability is poor. At the same time, the technology for preparing CPL materials based on supramolecular hydrogels of cucurbitacin is rare, especially in the preparation of white light CPL materials.

[0005] The present invention aims to study a material with low production cost, simple preparation method, and the ability to effectively integrate multiple light sources in a cucurbitacin hydrogel and maintain its CPL properties. Summary of the invention

[0006] In order to achieve the above technical objectives, the present invention provides a supramolecular hydrogel based on decamethyl five-membered cucurbitacin and a preparation method and application thereof.

[0007] This is achieved specifically through the following technical solutions:

[0008] The first object of the present invention is to provide: a supramolecular hydrogel based on a decamethyl five-membered cucurbitacin ring is composed of a decamethyl five-membered cucurbitacin ring (abbreviated as Me 10 Q[5]) and 2,2'-diamino-1,1'-binaphthyl hydrochloride (abbreviated as BINAM).

[0009] The BINAM is prepared by dissolving 2,2'-diamino-1,1'-binaphthyl in hydrochloric acid and freeze-drying the mixture.

[0010] The 2,2'-diamino-1,1'-binaphthyl hydrochloride is R-2,2'-diamino-1,1'-binaphthyl hydrochloride (referred to as R-BINAM) or S-2,2'-diamino-1,1'-binaphthyl hydrochloride (referred to as S-BINAM).

[0011] The second object of the present invention is to provide: a method for preparing the supramolecular hydrogel based on the decamethyl five-membered cucurbitacin, comprising the following steps:

[0012] (1) With water as solvent, add Me 10 Q[5] and BINAM are heated and dissolved to prepare Me 10 Q[5] aqueous solution and BINAM aqueous solution;

[0013] (2) Me 10 The Q[5] aqueous solution and the BINAM aqueous solution were mixed and heated to 75°C to obtain a transparent solution, ethanol was added while hot, and then slowly cooled to room temperature to form a supramolecular hydrogel based on a decamethyl five-membered cucurbitacin.

[0014] The mass concentration of BINAM in the transparent solution is 0.23-1.4 wt %.

[0015] Me 10 The mass concentration of Q[5] is 0.38-2.43wt%.

[0016] The volume concentration of ethanol in the transparent solution is 10-35%.

[0017] Further preferably, the mass concentration of (R / S)-BINAM in the transparent solution is 0.85wt%, Me 10 The mass concentration of Q[5] is 1.45wt%.

[0018] The third object of the present invention is to provide: application of the supramolecular hydrogel based on decamethyl five-membered cucurbitacin in the preparation of white light CPL materials.

[0019] The white light CPL material is prepared by mixing sulforhodamine B (denoted as S-RhB) with a Me 10 The supramolecular hydrogel of Q[5] is prepared by mixing.

[0020] The mass concentration of S-RhB in the white light CPL material is 0.008-0.012%.

[0021] Further preferably, the mass concentration of S-RhB in the white light CPL material is 0.01%.

[0022] Beneficial effects:

[0023] The synthesis method of the present invention has simple steps and low synthesis cost. 10 Q[5] is the main solution and BINAM is the guest solution, which solves the 10 The dispersion problem of Q[5] in the solution and the addition of ethanol reduced the possibility of fluorescence aggregation quenching.

[0024] The present invention is based on Me 10 The supramolecular hydrogel of Q[5] has good stability and mechanical properties, and improves the luminescence efficiency and CPL signal stability. The supramolecular hydrogel prepared by the present invention has color-adjustable and controllable CPL characteristics. Through supramolecular co-assembly, the molecular chirality of the guest can be transformed into the supramolecular chirality of the host-guest complex, and CPL luminescence and high luminescence asymmetry factor can be achieved at the same time.

[0025] The present invention is based on Me 10 After the introduction of the fluorescent dye sulfonyl rhodamine B (S-RhB), the supramolecular hydrogel of Q[5] can act as a receptor for fluorescence resonance energy transfer (FRET) and realize Me 10 The chirality transfer of Q[5] / (R / S)-BINAM complex can produce tunable emission color, which can be used to prepare white light CPL materials. It is expected that cucurbitacin hydrogels can be used to prepare white light CPL materials, which will broaden the scope of application of cucurbitacin. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 For different equivalents of Me 10 In the presence of Q[5], (R / S)-BINAM in aqueous solution 1 HNMR titration spectroscopy;

[0027] Figure 2 For (R / S)-BINAM and Me 10Job's plot of Q[5] (UV-vis absorbance at 235 nm in aqueous solution, C (R / S)-BINAM +C Me10Q[5] =10μM)

[0028] Figure 3 For Me 10 Q[5] UV-visible absorption spectrum titration diagram of (R / S)-BINAM supramolecular hydrogel;

[0029] Figure 4 For Me 10 Q[5] Quantum chemical theoretical calculation diagram of the two assembly modes of (R / S)-BINAM supramolecular hydrogel; (a) Me 10 Q[5] / R-BINAM; (b)Me 10 Q[5] / S-BINAM.

[0030] Figure 5 For Me 10 Dynamic oscillatory rheological properties of Q[5] / (R / S)-BINAM supramolecular hydrogel at 25°C: (a) Storage modulus and loss modulus measured by strain amplitude sweep; (b) Complex viscosity and loss angle tanδ measured by strain amplitude sweep; (c) Storage modulus and loss modulus measured by frequency sweep; (d) Complex viscosity and loss angle tanδ measured by frequency sweep;

[0031] Figure 6 is the Me in the presence of different contents of S-RhB 10 Fluorescence and color change diagram of Q[5] / (R / S)-BINAM hydrogel: (a) shows the fluorescence and color change of Me in the presence of different contents of S-RhB. 10 Fluorescence spectrum of Q[5] / (R / S)-BINAM supramolecular hydrogel; (b) is the CIE coordinate; (c) is the color change of the gel under ultraviolet light irradiation, where 0% to 0.09% in (a) corresponds to a1 to a6 in (b) and (c);

[0032] Figure 7 For Me 10 Circular dichroism spectrum (CD spectrum) of Q[5] / (R / S)-BINAM supramolecular hydrogel; (a) is Me 10 Q[5] / (R / S)-BINAM supramolecular hydrogel, (b) Me doped with 0.01% S-RhB 10 Q[5] / (R / S)-BINAM supramolecular hydrogel;

[0033] Figure 8 For Me 10CPL spectra of Q[5] / (R / S)-BINAM supramolecular hydrogel; (a) Me 10 CPL spectrum of Q[5] / (R / S)-BINAM supramolecular hydrogel; (b)Me 10 Luminescence asymmetry factor g of Q[5] / (R / S)-BINAM supramolecular hydrogel lum (c) Me doped S-RhB 10 CPL spectra of Q[5] / (R / S)-BINAM supramolecular hydrogel; (d) S-RhB-doped)Me 10 Luminescence asymmetry factor g of Q[5] / (R / S)-BINAM supramolecular hydrogel lum value. DETAILED DESCRIPTION

[0034] The specific embodiments of the present invention are further described in detail below, but the present invention is not limited to these embodiments, and any improvement or substitution based on the basic spirit of the present embodiment still falls within the scope of protection required by the claims of the present invention.

[0035] Example 1

[0036] A Me-based 10 The method for preparing the supramolecular hydrogel of Q[5] comprises the following steps:

[0037] (1) Add Me to water 10 Q[5] was heated at 75°C and slowly stirred until dissolved to obtain 4 mM Me 10 Q[5] aqueous solution;

[0038] (2) Weigh a certain amount of R-2,2'-diamino-1,1'-binaphthyl, dissolve it in 6M HCl and freeze-dry it to obtain (R)-2,2'-diamino-1,1'-binaphthyl hydrochloride (referred to as (R / S)-BINAM), then add R-BINAM to water, heat it at 60°C, and slowly stir it until it dissolves, to obtain an 8 mM R-BINAM aqueous solution;

[0039] (3) Me 10 The Q[5] aqueous solution and the R-BINAM aqueous solution were mixed in a volume ratio of 1:1 and heated to 75°C to obtain a transparent solution. 35% (v / v) ethanol was added to the transparent solution while it was hot, and then slowly cooled to room temperature to form a supramolecular hydrogel. 10 The mass concentration of Q[5] is 0.38%, and the mass concentration of R-BINAM is 0.23%.

[0040] Example 2

[0041] A method for preparing a supramolecular hydrogel based on a decamethyl five-membered cucurbitacin comprises the following steps:

[0042] (1) Add Me to water 10 Q[5] was heated at 75°C and slowly stirred until dissolved to obtain 4 mM Me 10 Q[5] aqueous solution;

[0043] (2) Weigh a certain amount of S-2,2'-diamino-1,1'-binaphthyl, dissolve it in 6M HCl and freeze-dry it to obtain S-2,2'-diamino-1,1'-binaphthyl hydrochloride (referred to as (R / S)-BINAM), then add S-BINAM to water, heat it at 60°C, and slowly stir it until it dissolves, to obtain an 8 mM S-BINAM aqueous solution;

[0044] (3) Me 10 The Q[5] aqueous solution and the S-BINAM aqueous solution were mixed in a ratio of 1:1 and heated to 75°C to obtain a transparent solution. 35% (v / v) ethanol was added to the transparent solution, and then slowly cooled to room temperature to form a supramolecular hydrogel. 10 The mass concentration of Q[5] is 0.38%, and the mass concentration of S-BINAM is 0.23%.

[0045] Example 3

[0046] A method for preparing a supramolecular hydrogel based on a decamethyl five-membered cucurbitacin comprises the following steps:

[0047] (1) Add Me to water 10 Q[5] was heated at 75°C and slowly stirred until dissolved to obtain 25 mM Me 10 Q[5] aqueous solution;

[0048] (2) Weigh a certain amount of R-2,2'-diamino-1,1'-binaphthyl, dissolve it in 6M HCl and freeze-dry it to obtain R-2,2'-diamino-1,1'-binaphthyl hydrochloride (R-BINAM), then add R-BINAM to water, heat it at 60°C, and slowly stir it until it dissolves, to obtain a 50 mM R-BINAM aqueous solution;

[0049] (3) Me 10 The Q[5] aqueous solution and the R-BINAM aqueous solution were mixed in a ratio of 1:1 and heated to 75°C to obtain a transparent solution. 35% (v / v) ethanol was added to the transparent solution, and then slowly cooled to room temperature to form a supramolecular hydrogel. 10The mass concentration of Q[5] is 2.43%, and the mass concentration of R-BINAM is 1.42%.

[0050] Example 4

[0051] A method for preparing a supramolecular hydrogel based on a decamethyl five-membered cucurbitacin comprises the following steps:

[0052] (1) Add Me to water 10 Q[5] was heated at 75°C and slowly stirred until dissolved to obtain 25 mM Me 10 Q[5] aqueous solution;

[0053] (2) Weigh a certain amount of S-2,2'-diamino-1,1'-binaphthyl, dissolve it in 6M HCl and freeze-dry it to obtain S-2,2'-diamino-1,1'-binaphthyl hydrochloride (referred to as S-BINAM), then add S-BINAM to water, heat it at 60°C, and slowly stir it until it dissolves, to obtain a 50 mM S-BINAM aqueous solution;

[0054] (3) Me 10 The Q[5] aqueous solution and the S-BINAM aqueous solution were mixed in a ratio of 1:1 and heated to 75°C to obtain a transparent solution. 35% (v / v) ethanol was added to the transparent solution, and then slowly cooled to room temperature to form a supramolecular hydrogel. 10 The mass concentration of Q[5] is 2.43%, and the mass concentration of S-BINAM is 1.42%.

[0055] Example 6

[0056] A method for preparing a supramolecular hydrogel based on a decamethyl five-membered cucurbitacin comprises the following steps:

[0057] (1) Add Me to water 10 Q[5] was heated at 75°C and slowly stirred until dissolved to obtain 15 mM Me 10 Q[5] aqueous solution;

[0058] (2) Weigh a certain amount of R-2,2'-diamino-1,1'-binaphthyl, dissolve it in 6M HCl and freeze-dry it to obtain R-2,2'-diamino-1,1'-binaphthyl hydrochloride (R-BINAM), then add R-BINAM to water, heat it at 60°C, and slowly stir it until it dissolves, to obtain a 30 mM R-BINAM aqueous solution;

[0059] (3) Me 10The Q[5] aqueous solution and the R-BINAM aqueous solution were mixed in volume ratios of 0, 1:10, 1:5, 3:10, 2:5, 1:2, and 1:1 and heated to 75°C to obtain a transparent solution;

[0060] (4) Select Me in a transparent solution 10 The mass concentration of Q[5] is 1.45%, and the mass concentration of R-BINAM is 0.85%. 35% (v / v) ethanol is added to the mixture while hot, and then the mixture is slowly cooled to room temperature to form Me 10 Q[5] / R-BINAM supramolecular hydrogel;

[0061] (5) To the Me obtained in the above step 10 A series of CPL materials were prepared by doping different amounts of sulfonyl rhodamine B (denoted as S-RhB) into Q[5] / R-BINAM supramolecular hydrogels; the doping amounts of S-RhB were 0%, 0.01%, 0.03%, 0.05%, 0.07%, and 0.09% of the mass of R-BINAM;

[0062] (6) According to the same operation method and process parameters, R-BINAM was replaced by S-BINAM to prepare Me10Q[5] / S-BINAM supramolecular hydrogel and CPL material;

[0063] (7) Detection:

[0064] 1H NMR spectra were recorded in D 2 O at 20° C. using a JEOL JNM-ECZ400s spectrometer. Ultraviolet-visible (UV-Vis) absorption spectra of the hydrate and the host-guest complex were recorded at 25° C. using a UV-2700 spectrophotometer (Shimadzu, Japan).

[0065] Dynamic oscillatory rheological properties tests were performed using an Ares G2 (TA Instruments, USA) controlled strain rheometer at 25 °C. Fluorescence spectra were recorded on a RF-6000 fluorescence spectrometer (Shimadzu, Japan). 10The CD and CPL spectra of the Q[5] / (R / S)-BINAM supramolecular hydrogel system were measured at room temperature using an Applied Photophysics Chirascan circular dichroism spectrometer (Applied Photophysics Ltd, UK) and a JASCO CPL-300 spectrometer, respectively. The fluorescence quantum yield was measured using an absolute PL quantum yield spectrometer C11347 equipped with a 150W steady-state xenon lamp. The fluorescence lifetime was measured using a high-precision TAUC11367 fluorescence lifetime measurement instrument equipped with a nanosecond pulsed LED light source. The structure was optimized using the Gaussian 16 software package at the B3LYP / 6-31+G*(d,p) theoretical level.

[0066] (7) The results are as follows:

[0067] Figure 1 (a) is Me in different equivalents 10 In the presence of Q[5], R-BINAM in aqueous solution 1 H NMR titration spectrum, Figure 1 (b) is Me at different equivalents 10 In the presence of Q[5], S-BINAM in aqueous solution 1 H NMR titration spectrum, as shown in the figure, in Me 10 In the presence of Q[5], the proton resonance of (R / S)-BINAM shifts downfield. 10 When the molar ratio of Q[5] to (R / S)-BINAM reaches 1:2, the proton H a The resonance of the proton H b The resonance of Me is shifted downfield by 0.39 ppm. These changes in chemical shifts are consistent with an interaction model in which the (R / S)-BINAM molecule is unable to enter the cavity and instead resides in the Me 10 On the other hand, (R / S)-BINAM and Me 10 The interaction between the two molecules leads to a broadening of the guest resonance signals to varying degrees, which is associated with the formation of a loosely bound complex. The broadening of the resonance signals indicates the presence of a relatively fast exchange process on the NMR time scale.

[0068] Figure 2 (a) is R-BINAM and Me 10 Job's graph of Q[5], Figure 2 (b) S-BINAM and Me 10 Job's diagram of Q[5] (UV-visible absorption spectrum at 235 nm in aqueous solution, C (R / S)-BINAM +CMe10Q[5] =10 μM), a series of solutions were prepared by changing the molar ratio of the two components. 10 Q[5]: (R / S)-BINAM combinations are 0:10, 1:9, 2:8, 3:7, 4:6, up to 10:0. max The UV-Vis spectroscopic titration was performed at 235 nm. The UV-Vis absorption spectra of the solutions were recorded at 25 °C using a UV-2700 spectrophotometer (Shimadzu, Japan). The host-guest stoichiometric ratio was confirmed by Job's diagram. The absorbance change (ΔA) at C guest / (C guest +C host ) value is 2:3, the maximum change occurs, indicating that Me 10 The molar ratio of Q[5] to (R / S)-BINAM host-guest binding is 1:2.

[0069] Figure 3 (a) for Me 10 Q[5] UV-visible absorption spectrum titration diagram of R-BINAM supramolecular hydrogel, Figure 3 (b) for Me 10 Q[5] UV-visible absorption spectrum titration of S-BINAM supramolecular hydrogel; in addition, UV-vis titration was performed to determine the binding constant of the host-guest interaction and the absorption values ​​were curve fitted using formula (1) to determine the primary and secondary binding constants of the supramolecular interaction, Me 10 Q[5] and R-BINAM binding constant K a1 =5.38×10 4 L / mol and K a2 =1.36×10 6 L / mol,Me 10 Q[5] and S-BINAM binding constant K a1 =4.81×10 4 L / mol and K a2 =5.22×10 6 L / molSee Figure 3 .

[0070]

[0071] Figure 4 For Me 10 Q[5] Quantum chemical theoretical calculation diagram of two assembly modes of (R / S)-BINAM supramolecular hydrogel; Me 10 The optimized complex of 1:2 supramolecular assembly of Q[5] and (R / S)-BINAM showed that Me 10The carbonyl group at the Q[5] end forms hydrogen bonds with the two amino groups of (R / S)-BINAM—one amino group is located between the Me 10 The Q[5] carbonyl port is located at the center, and the other is located at the Me 10 The edge of the carbonyl port of Q[5]. The interaction distance between the carbonyl oxygen atom and the amino nitrogen atom was measured to be between 2.7 and The binding energy (E binding ) can be defined as the difference between the total energy of the host-guest complex and the total energy of the separated host and guest molecules, usually expressed by formula (2);

[0072] E binding =E host-guestcomplex -(E host +E guest ) (2)

[0073] Where: E host-guestcomplex is the total energy of the host-guest complex, E host is the total energy of the host molecule, E guest is the total energy of the guest molecule.

[0074] E binding Calculated as Me 10 Q[5] / S-BINAM has -124.31 kcal / mol and Me 10 Q[5] / R-BINAM -126.90 kcal / mol. binding The small difference shows that Me 10 The assembled structures of Q[5] and R-BINAM and S-BINAM have similar stability. binding Numerical proof of Me 10 The assembly process of Q[5] / (R / S)-BINAM should occur spontaneously.

[0075] Figure 5 For Me 10 Dynamic oscillatory rheological properties of Q[5] / (R / S)-BINAM supramolecular hydrogel at 25°C: (a) Storage modulus (G') and loss modulus (G") measured by strain amplitude sweep; (b) Complex viscosity and loss tangent (tanδ) measured by strain amplitude sweep; (c) Storage modulus (G') and loss modulus (G") measured by frequency sweep; (d) Complex viscosity and loss tangent (tanδ) measured by frequency sweep; Figure 1 It can be seen that the Me 10 Mechanical properties of Q[5] / (R / S)-BINAM supramolecular hydrogels. Strain-dependent oscillatory rheological analysis ( Figure 5 a and 5b) show a broad linear viscoelastic region, Me10 Q[5] / (R / S)-BINAM supramolecular hydrogel deviates from linear viscoelastic behavior at about 3% strain. Outside this strain range, the significant decrease in storage modulus (G') and loss modulus (G") indicates the collapse of the gel network. Frequency dependence analysis shows that in the low-frequency region, both G' and G" are independent of frequency, and G' is always greater than G", exhibiting solid-like behavior. These results indicate that in Me 10 A mechanically interconnected network was formed in the Q[5] / (R / S)-BINAM supramolecular hydrogel ( Figure 5 c). In addition, the prepared supramolecular hydrogel exhibited linear shear thinning behavior with relatively low mechanical loss (Me 10 Q[5] / S-BINAM≈0.5 and Me10Q[5] / R-BINAM≈0.7)( Figure 5 d), a value less than 1 indicates that the entire system tends to have solid-like properties.

[0076] Figure 6 is the Me in the presence of different contents of S-RhB 10 Fluorescence and color change diagram of Q[5] / (R / S)-BINAM hydrogel, where (a) is the fluorescence and color change of Me in the presence of different amounts of S-RhB. 10 Fluorescence spectrum of Q[5] / (R / S)-BINAM supramolecular hydrogel; (b) is the CIE coordinate; (c) is the color change of the gel under ultraviolet light irradiation, where 0% to 0.09% in (a) corresponds to a1 to a6 in (b) and (c); Figure 6 It can be seen that: when the amount of S-RhB doping increases gradually, 10 In the Q[5] / (R / S)-BINAM supramolecular hydrogel, the fluorescence emission at 520 nm of the hydrogel weakened and shifted to a shorter wavelength, and the new fluorescence emission at 600 nm gradually increased and red-shifted ( Figure 6 a) The emission at 600 nm can be attributed to the fluorescence of S-RhB, indicating that Me 10 The Q[5] / (R / S)-BINAM supramolecular hydrogel and S-RhB have an effective energy transfer. When the S-RhB doping amount is 0.09%, the fluorescence resonance energy transfer efficiency (Φ ET ) reached 50.3%. As the S-RhB concentration increased in the range of 0-0.09%, Me 10 The fluorescence emission of Q[5] / (R / S)-BINAM supramolecular hydrogel under 365nm ultraviolet light changes from blue to red (a1-a6, Figure 6 b and 6c). When doped with 0.01% S-RhB, the fluorescence emission of the supramolecular hydrogel is close to white light, with CIE coordinates of (0.31, 0.32). 10The energy transfer process between Q[5] / (R / S)-BINAM supramolecular hydrogel and S-RhB dye. We measured the photoluminescence quantum yield of supramolecular hydrogels doped with 0.01% S-RhB and without 0.01% S-RhB. and fluorescence lifetime (τ), as shown in Table 1, in the absence of S-RhB, Me 10 Q[5] / R-BINAM and Me 10 Quantum yield of Q[5] / S-BINAM at 520nm After doping with 0.01% S-RhB, Me 10 Q[5] / R-BINAM and Me 10 Quantum yield of Q[5] / S-BINAM at 520nm The quantum yield at 600nm dropped to 2.4% and 2.5%. The fluorescence lifetime (τ) was increased to 1.2% and decreased to 4.63 ns and 4.64 ns, further demonstrating the effective energy transfer mechanism.

[0077] Table 1 Me doped with 0.01% S-RhB and without S-RhB 10 Photoluminescence quantum yield of Q[5] / (R / S)-BINAM hydrogel and fluorescence lifetime (τ) (Ex = 340nm)

[0078]

[0079] Figure 7 For Me 10 Circular dichroism spectrum (CD spectrum) of Q[5] / (R / S)-BINAM supramolecular hydrogel; (a) is Me 10 Q[5] / (R / S)-BINAM supramolecular hydrogel, (b) Me doped with 0.01% S-RhB 10 Q[5] / (R / S)-BINAM supramolecular hydrogel; Figure 7 It can be known that: Me 10 Q[5] / R-BINAM supramolecular hydrogel exhibits an obvious negative Cotton effect, while Me 10 Q[5] / S-BINAM supramolecular hydrogel exhibits an obvious positive Cotton effect, with the two spectra intersecting at 241 nm and 284 nm ( Figure 7 a) Me 10The mirror image relationship of the CD spectra of Q[5] / (R / S)-BINAM supramolecular hydrogels indicates that the supramolecular chirality of the gel is related to the chirality of the component (R / S)-BINAM. Although S-RhB itself is achiral, after being doped into the supramolecular hydrogel, (R / S)-BINAM is induced to produce supramolecular chirality. Therefore, a chiral signal at 550nm is observed in the CD spectrum ( Figure 7 b), indicating that the chirality changes from Me 10 Q[5] / (R / S)-BINAM is effectively transferred to S-RhB. The results show that the chiral signal of S-RhB at 550nm is similar to that of Me 10 The chirality of Q[5] / (R / S)-BINAM is consistent, indicating that S-RhB and Me 10 Q[5] / (R / S)-BINAM together formed a chiral supramolecular hydrogel.

[0080] Figure 8 is the CPL spectrum and luminescence asymmetry factor (g lum ); (a) is Me 10 CPL spectrum of Q[5] / (R / S)-BINAM supramolecular hydrogel; (b) Me 10 Q[5] / (R / S)-BINAM supramolecular hydrogel lum ; (c) Me doped with 0.01% S-RhB 10 CPL spectrum of Q[5] / (R / S)-BINAM supramolecular hydrogel; (d) Me doped with 0.01% S-RhB 10 Q[5] / (R / S)-BINAM supramolecular hydrogel lum ; CPL emission is a manifestation of the chirality of the excited state of chiral luminescent materials, which requires the coexistence of chirality and fluorescence emission, such as Me 10 In Q[5] / (R / S)-BINAM supramolecular hydrogel, supramolecular chirality and emission with significant energy transfer were observed. Figure 8 As shown in a, Me 10 The Q[5] / S-BINAM supramolecular hydrogel exhibited a left-handed CPL signal at 520 nm, while Me 10 Q[5] / R-BINAM hydrogel exhibits right-handed CPL signals at the same wavelength, and the two supramolecular CPL emission directions are opposite. 10 The g of Q[5] / S-BINAM supramolecular hydrogel at 520 nm lum 1.16×10 -3 , and Me 10 Q[5] / R-BINAM supramolecular hydrogel lum =-1.2×10 -3( Figure 8 b) It is worth noting that Figure 8 As shown in c and 8d, after doping with 0.01% S-RhB, the hydrogel generated a new CPL signal at 620nm, while the CPL signal at 520nm weakened, which indicated that Me 10 The circular polarization energy of Q[5] / (R / S)-BINAM supramolecular hydrogel was effectively transferred to S-RhB, which was consistent with the fluorescence energy transfer evidence. 10 The g of Q[5] / R-BINAM supramolecular hydrogel at 520 nm lum becomes -1.07×10 -3 , reaching -1.35×10 at 620nm -3 , Me 10 The Q[5] / S-BINAM supramolecular hydrogel has a wavelength of 1.26×10 -3 , at 620nm is 1.56×10 -3 . g lum This is within the same order of magnitude as typical chiral supramolecular luminescent materials, indicating that the chiral transfer is stable and reliable.

Claims

1. A supramolecular hydrogel based on a decamethyl five-membered cucurbitacin ring, characterized in that: The decamethyl five-membered cucurbitacin-based supramolecular hydrogel is prepared from decamethyl five-membered cucurbitacin and 2,2'-diamino-1,1'-binaphthyl hydrochloride.

2. A supramolecular hydrogel based on a decamethyl five-membered cucurbitacin ring as claimed in claim 1, characterized in that: The 2,2'-diamino-1,1'-binaphthyl hydrochloride is R-2,2'-diamino-1,1'-binaphthyl hydrochloride or S-2,2'-diamino-1,1'-binaphthyl hydrochloride.

3. A method for preparing a supramolecular hydrogel based on a decamethyl five-membered cucurbitacin ring as claimed in claim 1 or 2, characterized in that: The steps include: (1) With water as solvent, add Me 10 Q[5] and BINAM are heated and dissolved to prepare Me 10 Q[5] aqueous solution and BINAM aqueous solution; (2) Me 10 The Q[5] aqueous solution and the BINAM aqueous solution were mixed and heated to 75°C to obtain a transparent solution, ethanol was added while hot, and then slowly cooled to room temperature to form a supramolecular hydrogel.

4. A method for preparing a supramolecular hydrogel based on a decamethyl five-membered cucurbitacin as claimed in claim 3, characterized in that: The mass concentration of BINAM in the transparent solution is 0.23-1.4 wt %.

5. The method for preparing a supramolecular hydrogel based on a decamethyl five-membered cucurbitacin as claimed in claim 3, characterized in that: Me 10 The mass concentration of Q[5] is 0.38-2.43wt%.

6. The method for preparing a supramolecular hydrogel based on a decamethyl five-membered cucurbitacin as claimed in claim 3, characterized in that: The BINAM is prepared by dissolving 2,2'-diamino-1,1'-binaphthyl in hydrochloric acid and freeze-drying the mixture.

7. The method for preparing a supramolecular hydrogel based on a decamethyl five-membered cucurbitacin as claimed in claim 3, characterized in that: The volume concentration of ethanol in the transparent solution is 10-35%.

8. Use of a decamethyl five-membered cucurbitacin-based supramolecular hydrogel as claimed in any one of claims 1 to 2 or a decamethyl five-membered cucurbitacin-based supramolecular hydrogel prepared by the preparation method as claimed in any one of claims 3 to 7 in the preparation of white light CPL materials.

9. The use according to claim 8, characterized in that The white light CPL material is prepared by mixing sulforhodamine B with a supramolecular hydrogel based on a decamethyl five-membered cucurbitacin.

10. The use according to claim 9, characterized in that The mass concentration of sulforhodamine B in the white light CPL material is 0.008-0.012%.

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