A supramolecular hydrogel based on decamethyl pentaguanamine and a preparation method and application thereof

Abstract

The application belongs to the technical field of supramolecular hydrogel preparation, and particularly relates to a supramolecular hydrogel based on decamethyl five-membered cucurbituril and a preparation method and application thereof. The supramolecular hydrogel based on decamethyl five-membered cucurbituril is made of decamethyl five-membered cucurbituril and 2,2'-diamino-1,1'-binaphthalene hydrochloride. The synthesis method is simple, the synthesis cost is low, and the synthesis process is green. The application uses decamethyl five-membered cucurbituril as a host solution, 2,2'-diamino-1,1'-binaphthalene hydrochloride as a guest solution, and the addition of ethanol reduces the possibility of fluorescence aggregation quenching. After the introduction of fluorescent dye sulfonyl rhodamine B, it can be used as a receptor for fluorescence resonance energy transfer, and the chiral transfer of the decamethyl five-membered cucurbituril and 2,2'-diamino-1,1'-binaphthalene hydrochloride complex in the hydrogel system is realized to produce adjustable emission color, so that the preparation of white light circularly polarized luminescent materials is realized.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of supramolecular hydrogel preparation, and particularly relates to a supramolecular hydrogel based on decamethyl pentaguanide and a preparation method and application thereof. BACKGROUND

[0002] Circularly polarized luminescence (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 pentaguanide is a macrocyclic host molecule with a special cavity structure, which can be co-assembled with guest molecules to prepare CPL materials. The main preparation methods include metal ion coordination, chiral template method, and chiral inducer doping of non-chiral conjugated polymers. However, the random motion in solution and the influence of oxygen and other quenching factors will limit the fluorescence emission, thereby affecting the luminescent efficiency and stability of the circularly polarized luminescence material. Moreover, the application of hydrogel in the preparation of CPL materials is not widespread. Existing white CPL gel materials often need to go through complex organic synthesis steps to connect chiral sources and luminophores through covalent bonds.

[0003] Although the invention patent with the publication number CN111410953A discloses a circularly polarized luminescence supramolecular gel and a preparation method and application thereof, a C2 symmetric phenylalanine derivative is used as a chiral gelator, and a fused ring aromatic hydrocarbon or a benzofused heterocyclic compound is used as a non-chiral fluorescent molecule. The chiral gelator and the non-chiral fluorescent molecule are co-assembled through intermolecular hydrogen bonds and π-π interactions to obtain a circularly polarized luminescence supramolecular hydrogel. However, this method uses acetonitrile solvent, which is more toxic and more expensive than water. Moreover, it does not use cucurbituril as a host molecule. Although the invention patent with the publication number CN118405967A mentions that classical supramolecular macrocyclic host molecules such as pillararenes, calixarenes and cucurbiturils can be used to prepare circularly polarized luminescence materials, it does not specifically disclose a method for producing circularly polarized luminescence gels using cucurbituril as a raw material.

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

[0005] The present application aims to study a material with low production cost, simple preparation method, and the ability to effectively integrate multiple light sources in a cucurbituril hydrogel while maintaining its CPL characteristics. SUMMARY

[0006] The present application discloses a supramolecular hydrogel based on ten-methyl five-membered cucurbituril, a preparation method and application thereof.

[0007] The present application is achieved by the following technical solutions.

[0008] The present application provides a supramolecular hydrogel based on ten-methyl five-membered cucurbituril, which is made of ten-methyl five-membered cucurbituril (abbreviated as Me 10 Q[5]) and 2,2'-diamino-1,1'-binaphthyl hydrochloride (abbreviated as BINAM).

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

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

[0011] The present application provides a preparation method of the supramolecular hydrogel based on ten-methyl five-membered cucurbituril, which comprises the following steps:

[0012] (1) adding Me 10 Q[5] and BINAM into water as a solvent respectively and heating to dissolve, to prepare Me 10 Q[5] aqueous solution and BINAM aqueous solution respectively;

[0013] (2) mixing the Me 10 Q[5] aqueous solution and the BINAM aqueous solution, heating to 75 DEG C to obtain a transparent solution, adding ethanol while hot, and then slowly cooling to room temperature to form the supramolecular hydrogel based on ten-methyl five-membered cucurbituril.

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

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

[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 0.85 wt%, and the mass concentration of Me 10 Q[5] is 1.45 wt%.

[0018] The third object of the present application is to provide an application of the supermolecular hydrogel based on decamethyl five-membered cucurbituril in preparing a white light CPL material.

[0019] The white light CPL material is prepared by mixing sulfonated rhodamine B (denoted as S-RhB) with the supermolecular hydrogel based on Me 10 Q[5].

[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 synthetic method of the present application is simple in steps and low in cost, and the present application utilizes Me 10 Q[5] as a host solution and BINAM as a guest solution, solving the dispersion problem of BINAM and Me 10 Q[5] in solution, and the addition of ethanol reduces the possibility of fluorescence aggregation quenching.

[0024] The supermolecular hydrogel based on Me 10 Q[5] of the present application has good stability and mechanical properties, improves the luminous efficiency and CPL signal stability, and the supermolecular hydrogel prepared by the present application has color-adjustable and controllable CPL characteristics, and through supermolecular co-assembly, the molecular chirality of the guest can be changed to the supermolecular chirality of the host-guest complex, and CPL emission and high luminescent asymmetry factor can be realized.

[0025] The supermolecular hydrogel based on Me 10 Q[5] of the present application can act as a receptor of fluorescence resonance energy transfer (FRET) after introducing the fluorescent dye sulfonated rhodamine B (S-RhB), and can realize the chirality transfer of Me 10 Q[5] / (R / S)-BINAM complex in the hydrogel system to produce adjustable emission color, and can be used for preparing a white light CPL material, and is expected to realize the preparation of a white light CPL material by cucurbituril hydrogel, and widens the range of application of cucurbituril. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 To study the CPL properties of (R / S)-BINAM in aqueous solution in the presence of Me 10 Q[5] at different equivalents; 1 HNMR titration spectrum;

[0027] Figure 2 To study the CPL properties of (R / S)-BINAM in aqueous solution in the presence of Me 10Job's plot of Q[5] (UV-Vis absorbance at 235 nm in aqueous solution, C (R / S)-BINAM + C Me10Q[5] = 10 μM)

[0028] Figure 3 Me 10 UV-Vis absorption titration plot of Q[5] on (R / S)-BINAM supramolecular hydrogel;

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

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

[0031] Figure 6 Me 10 Fluorescence and color change plot of Q[5] / (R / S)-BINAM hydrogel: where (a) is Me 10 Fluorescence spectra of Q[5] / (R / S)-BINAM supramolecular hydrogel; (b) is CIE coordinates; (c) is color change of the gel under UV irradiation, where 0% to 0.09% in (a) corresponds to a1 to a6 in (b) and (c);

[0032] Figure 7 Me 10 Circular dichroism spectra (CD spectra) of Q[5] / (R / S)-BINAM supramolecular hydrogel; where (a) is Me 10 Q[5] / (R / S)-BINAM supramolecular hydrogel, (b) is Me 10 Q[5] / (R / S)-BINAM supramolecular hydrogel;

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

[0034] The specific embodiments of the present application are described in further detail below, but the present application is not limited to these embodiments, and any improvement or replacement within the basic spirit of the present embodiments still falls within the scope of the claims of the present application.

[0035] Example 1

[0036] A supramolecular hydrogel based on Me 10 A preparation method of a supramolecular hydrogel based on Me

[0037] (1) Me 10 Q[5] is added to water, heated at 75℃, and slowly stirred until dissolved to prepare a 4mM Me 10 Q[5] aqueous solution;

[0038] (2) A certain amount of R-2,2'-diamino-1,1'-binaphthyl is weighed, dissolved in 6M HCl and freeze-dried to prepare (R)-2,2'-diamino-1,1'-binaphthyl hydrochloride (denoted as (R / S)-BINAM), and then R-BINAM is added to water, heated at 60℃, and slowly stirred until dissolved to prepare an 8mM R-BINAM aqueous solution;

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

[0040] Example 2

[0041] A preparation method of a supramolecular hydrogel based on decamethyl pentaguanide, comprising the following steps:

[0042] (1) adding Me 10 Q[5] into water, heating at 75℃, slowly stirring until dissolved, to prepare a 4mM Me 10 Q[5] aqueous solution;

[0043] (2) weighing a certain amount of S-2,2'-diamino-1,1'-binaphthyl, dissolving in 6M HCl and freeze-drying to prepare S-2,2'-diamino-1,1'-binaphthyl hydrochloride (denoted as (R / S)-BINAM), then adding S-BINAM into water, heating at 60℃, slowly stirring until dissolved, to prepare an 8mM S-BINAM aqueous solution;

[0044] (3) mixing the Me 10 Q[5] aqueous solution and the S-BINAM aqueous solution according to a 1:1 ratio, heating to 75℃ to obtain a transparent solution, then adding 35% (v / v) ethanol into the transparent solution, and slowly cooling to room temperature to form a supramolecular hydrogel; the mass concentration of Me 10 Q[5] in the transparent solution is 0.38%, and the mass concentration of S-BINAM is 0.23%.

[0045] Example 3

[0046] A preparation method of a supramolecular hydrogel based on decamethyl pentaguanide, comprising the following steps:

[0047] (1) adding Me 10 Q[5] into water, heating at 75℃, slowly stirring until dissolved, to prepare a 25mM Me 10 Q[5] aqueous solution;

[0048] (2) weighing a certain amount of R-2,2'-diamino-1,1'-binaphthyl, dissolving in 6M HCl and freeze-drying to prepare R-2,2'-diamino-1,1'-binaphthyl hydrochloride (denoted as R-BINAM), then adding R-BINAM into water, heating at 60℃, slowly stirring until dissolved, to prepare a 50mM R-BINAM aqueous solution;

[0049] (3) mixing the Me 10 Q[5] aqueous solution and the R-BINAM aqueous solution according to a 1:1 ratio, heating to 75℃ to obtain a transparent solution, then adding 35% (v / v) ethanol into the transparent solution, and slowly cooling to room temperature to form a supramolecular hydrogel; the mass concentration of Me 10The mass concentration of Q[5] is 2.43%, and the mass concentration of R-BINAM is 1.42%.

[0050] Example 4

[0051] A preparation method of a supramolecular hydrogel based on decamethyl pentaguanide, comprising the following steps:

[0052] (1) adding Me 10 Q[5] into water, heating at 75℃, and slowly stirring until dissolved to prepare a 25mM Me 10 Q[5] aqueous solution;

[0053] (2) weighing a certain amount of S-2,2'-diamino-1,1'-binaphthyl, dissolving it in 6M HCl and freeze-drying to prepare S-2,2'-diamino-1,1'-binaphthyl hydrochloride (denoted as S-BINAM), then adding S-BINAM into water, heating at 60℃, and slowly stirring until dissolved to prepare a 50mM S-BINAM aqueous solution;

[0054] (3) mixing the Me 10 Q[5] aqueous solution and the S-BINAM aqueous solution in a ratio of 1:1, heating to 75℃ to obtain a transparent solution, adding 35% (v / v) ethanol into the transparent solution, and then slowly cooling to room temperature to form a supramolecular hydrogel; the mass concentration of Me 10 Q[5] in the transparent solution is 2.43%, and the mass concentration of S-BINAM is 1.42%.

[0055] Example 6

[0056] A preparation method of a supramolecular hydrogel based on decamethyl pentaguanide, comprising the following steps:

[0057] (1) adding Me 10 Q[5] into water, heating at 75℃, and slowly stirring until dissolved to prepare a 15mM Me 10 Q[5] aqueous solution;

[0058] (2) weighing a certain amount of R-2,2'-diamino-1,1'-binaphthyl, dissolving it in 6M HCl and freeze-drying to prepare R-2,2'-diamino-1,1'-binaphthyl hydrochloride (denoted as R-BINAM), then adding R-BINAM into water, heating at 60℃, and slowly stirring until dissolved to prepare a 30mM R-BINAM aqueous solution;

[0059] (3) mixing the Me 10Q[5] aqueous solution and 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 transparent solutions;

[0060] (4) Me10Q[5] / R-BINAM supramolecular hydrogel was selected from the transparent solutions; 10 The mass concentration of Q[5] was 1.45%, and the mass concentration of R-BINAM was 0.85%. 35% (v / v) of ethanol was added into the mixture while hot, and slowly cooled to room temperature to form Me10Q[5] / R-BINAM supramolecular hydrogel. 10 Q[5] / R-BINAM supramolecular hydrogel;

[0061] (5) Me10Q[5] / R-BINAM supramolecular hydrogel obtained in the above step was mixed with 35% (v / v) of ethanol, and slowly cooled to room temperature to form Me10Q[5] / R-BINAM CPL material; 10 Q[5] / R-BINAM supramolecular hydrogel was mixed with different amounts of sulforhodamine B (denoted as S-RhB) to prepare a series of CPL materials; the doping amount of S-RhB was 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 D2O at 20°C using a JEOL JNM-ECZ400s spectrometer. The UV-Vis absorption spectra of the hydrates and host-guest complexes were recorded at 25°C using a UV-2700 spectrophotometer (Shimadzu, Japan).

[0065] Dynamic oscillatory rheological property tests were performed at 25°C using an Ares G2 (TA Instruments, USA) controlled-strain rheometer. Fluorescence spectra were recorded on an RF-6000 fluorescence spectrometer (Shimadzu, Japan). Me10Q[5] / R-BINAM CPL material was prepared by mixing Me10Q[5] / R-BINAM supramolecular hydrogel with 35% (v / v) of ethanol, and slowly cooling to room temperature. 10The CD and CPL spectra of Q[5] / (R / S)-BINAM supramolecular hydrogel systems 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 150 W steady-state xenon lamp. The fluorescence lifetime test was performed using a high-precision TA UC11367 fluorescence lifetime measurement instrument equipped with a nanosecond pulsed LED light source. The structures were optimized at the B3LYP / 6-31+G*(d, p) theoretical level using the Gaussian 16 software package.

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

[0067] Figure 1 (a) is the Job's plot of R-BINAM with Me 10 Q[5] in aqueous solution, 1 H NMR titration spectra, Figure 1 (b) is the Job's plot of S-BINAM with Me 10 Q[5] in aqueous solution, 1 H NMR titration spectra, as shown, Me 10 Q[5] is present, the proton resonance of (R / S)-BINAM all appears to shift to low field. When Me 10 Q[5] and (R / S)-BINAM reach a molar ratio of 1:2, the resonance of proton H a shifts to low field by 0.18 ppm, while the resonance of proton H b shifts to low field by 0.39 ppm. These changes in chemical shift are consistent with a model of interaction in which (R / S)-BINAM molecules cannot enter the cavity but are stopped at the port of Me 10 Q[5]. On the other hand, the interaction between (R / S)-BINAM and Me 10 Q5] causes the resonance signal of the guest to be broadened to varying degrees, which is related to the formation of a loosely bound complex. The broadening of the resonance signal indicates the presence of a relatively fast exchange process on the nuclear magnetic resonance time scale.

[0068] Figure 2 (a) is the Job's plot of R-BINAM with Me 10 Q[5], Figure 2 (b) is the Job's plot of S-BINAM with Me 10 Q[5] (UV-Vis absorption spectra at 235 nm in aqueous solution, C (R / S)-BINAM +CMe10Q[5] = 10 mM), a series of solutions were prepared by varying the molar ratio of the two components, obtaining Me 10 Q[5] in different molar ratios with (R / S)-BINAM in the range 0:10, 1 :9, 2:8, 3:7, 4:6, up to 10:0. UV-Vis spectra were recorded at 25 °C using a UV-2700 spectrophotometer (Shimadzu, Japan) at 235 nm. max = 10 mM), a series of solutions were prepared by varying the molar ratio of the two components, obtaining Me guest = 10 mM), a series of solutions were prepared by varying the molar ratio of the two components, obtaining Me guest = 10 mM), a series of solutions were prepared by varying the molar ratio of the two components, obtaining Me host = 10 mM), a series of solutions were prepared by varying the molar ratio of the two components, obtaining Me 10 = 10 mM), a series of solutions were prepared by varying the molar ratio of the two components, obtaining Me

[0069] Figure 3 (a) is the UV-Vis absorption spectrum titration of Me 10 Q[5] on R-BINAM supramolecular hydrogel, Figure 3 (b) is the UV-Vis absorption spectrum titration of Me 10 Q[5] on S-BINAM supramolecular hydrogel; in addition, UV-vis titration was carried out to determine the binding constant of the host-guest interaction and curve fitting of the absorption values was performed using equation (1) to determine the primary and secondary binding constants of the supramolecular interaction, Me 10 Q[5] with R-BINAM has a binding constant K a1 = 5.38 x 10 4 L / mol and K a2 = 1.36 x 10 6 L / mol, Me 10 Q[5] with S-BINAM has a binding constant K a1 = 4.81 x 10 4 L / mol and K a2 = 5.22 x 10 6 L / mol, as detailed in Figure 3 .

[0070]

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

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

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

[0074] E binding Calculate them as Me respectively 10 Q[5] / S-BINAM -124.31kcal / mol and Me 10 Q[5] / R-BINAM -126.90kcal / mol. E binding The small differences indicate that Me 10 Q[5] has similar stability to the assembly structures of R-BINAM and S-BINAM, E 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℃: (a) storage modulus (G') and loss modulus (G") obtained by strain amplitude scanning measurement; (b) complex viscosity and loss tangent (tanδ) obtained by strain amplitude scanning measurement; (c) storage modulus (G') and loss modulus (G") obtained by frequency scanning measurement; (d) complex viscosity and loss tangent (tanδ) obtained by frequency scanning measurement; Figure 1 It can be seen that Me was studied using a rheometer. 10 Mechanical properties of Q[5] / (R / S)-BINAM supramolecular hydrogel. Strain-dependent oscillatory rheological analysis ( Figure 5 a) and 5b) show a wider linear viscoelastic region, Me10 Q[5] / (R / S)-BINAM supramolecular hydrogels deviated from linear viscoelastic behavior at about 3% strain. Outside this strain range, a significant decrease in both storage modulus (G') and loss modulus (G") indicated the collapse of the gel network. Frequency-dependent analysis showed that in the low frequency region, both G' and G" were independent of frequency, and G' was always greater than G", exhibiting a solid-like behavior. These results indicated that a mechanically interlinked network was formed in Me 10 Q[5] / (R / S)-BINAM supramolecular hydrogels Figure 5 c). In addition, the prepared supramolecular hydrogels 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), which was less than 1, indicating that the whole system tended to the characteristics of a solid-like material.

[0076] Figure 6 To investigate the effect of S-RhB on the mechanical properties of Me 10 Fluorescence and color change of Q[5] / (R / S)-BINAM hydrogels in the presence of different amounts of S-RhB, where (a) is the fluorescence spectra of Me 10 Fluorescence spectra of Q[5] / (R / S)-BINAM supramolecular hydrogels; (b) is the CIE coordinates; (c) is the color change of the gel under UV irradiation, where 0% to 0.09% in (a) corresponds to a1 to a6 in (b) and (c); from Figure 6 It can be seen that as the amount of S-RhB doping in Me 10 In Q[5] / (R / S)-BINAM supramolecular hydrogels, the fluorescence emission of the hydrogel at 520 nm was weakened and shifted to shorter wavelengths, and a new fluorescence emission at 600 nm gradually increased and was red-shifted Figure 6 a). The luminescence at 600 nm can be attributed to the fluorescence of S-RhB, indicating that Me 10 Q[5] / (R / S)-BINAM supramolecular hydrogels and S-RhB undergo efficient energy transfer. When the doping amount of S-RhB is 0.09%, the fluorescence resonance energy transfer efficiency (Φ ET ) reaches 50.3%. As the concentration of S-RhB increases in the range of 0-0.09%, Me 10 The fluorescence emission of Q[5] / (R / S)-BINAM supramolecular hydrogels under 365 nm UV light changes from blue to red (a1-a6, Figure 6 b and 6c). At the same time, when 0.01% S-RhB is doped, the fluorescence emission of the supramolecular hydrogel approaches white light, with CIE coordinates of (0.31, 0.32). To further confirm Me 10The energy transfer process between Q[5] / (R / S)-BINAM supramolecular hydrogel and S-RhB dye, we measured the photoluminescence quantum yield of supramolecular hydrogel doped with 0.01% S-RhB and without doped with 0.01% S-RhB and fluorescence lifetime (τ), as shown in Table 1, Me 10 Q[5] / R-BINAM and Me 10 Q[5] / S-BINAM at 520 nm were 3.6% and 3.7%, respectively, and the fluorescence lifetime (τ) were 4.77 ns and 4.76 ns, respectively. After doped with 0.01% S-RhB, Me 10 Q[5] / R-BINAM and Me 10 Q[5] / S-BINAM at 520 nm dropped to 2.4% and 2.5%, and the quantum yield at 600 nm increased to 1.2%, and the average fluorescence lifetime (τ) dropped to 4.63 ns and 4.64 ns, further proving the effective energy transfer mechanism.

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

[0078]

[0079] Figure 7 Me 10 Circular dichroism spectrum (CD spectrum) of Me Q[5] / (R / S)-BINAM supramolecular hydrogel; (a) is Me 10 Q[5] / (R / S)-BINAM supramolecular hydrogel, (b) is Me doped with 0.01% S-RhB 10 Q[5] / (R / S)-BINAM supramolecular hydrogel; from Figure 7 It can be seen that Me 10 Q[5] / R-BINAM supramolecular hydrogel shows obvious negative Cotton effect, while Me 10 Q[5] / S-BINAM supramolecular hydrogel shows obvious positive Cotton effect, the two spectra intersect at 241 nm and 284 nm Figure 7 (a) Me 10The mirror image relationship of the CD spectrum of Q[5] / (R / S)-BINAM supramolecular hydrogel 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 550 nm was observed in the CD spectrum. Figure 7 b) indicates that chirality originates 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 550 nm is similar to that of Me. 10 The chirality of Q[5] / (R / S)-BINAM is consistent, indicating that S-RhB and Me are consistent. 10 Q[5] / (R / S)-BINAM together formed a chiral supramolecular hydrogel.

[0080] Figure 8 For CPL spectrum and luminescence asymmetry factor (g) lum ); where (a) is Me 10 (b) is the CPL spectrum of Q[5] / (R / S)-BINAM supramolecular hydrogel; 10 Q[5] / (R / S)-BINAM supramolecular hydrogel g lum (c) Me doped with 0.01% S-RhB 10 CPL spectrum of Q[5] / (R / S)-BINAM supramolecular hydrogel; (d) is Me doped with 0.01% S-RhB. 10 Q[5] / (R / S)-BINAM supramolecular hydrogel g lum CPL emission is a manifestation of the chirality of excited-state chiral light-emitting materials, requiring both chirality and fluorescence emission to coexist, such as Me. 10 Q[5] / (R / S)-BINAM supramolecular hydrogel, which exhibits supramolecular chirality and emission with significant energy transfer. Figure 8 As shown in a, Me 10 The Q[5] / S-BINAM supramolecular hydrogel exhibits a left-handed CPL signal at 520 nm, while Me 10 Q[5] / R-BINAM hydrogels exhibit right-handed CPL signals at the same wavelength, while the supramolecular CPL emission directions of the two are opposite. 10 Q[5] / S-BINAM supramolecular hydrogel at 520 nm g lum 1.16×10 -3 And Me 10 Q[5] / R-BINAM supramolecular hydrogel g lum -1.2×10 -3( Figure 8 b). It is worth noting that, as Figure 8 As shown in c and 8d, after doping with 0.01% S-RhB, the hydrogel generates a new CPL signal at 620 nm, while the CPL signal weakens at 520 nm, indicating that Me 10 The circular polarization energy of the Q[5] / (R / S)-BINAM supramolecular hydrogel was efficiently transferred to S-RhB, consistent with evidence of fluorescence energy transfer. With the energy transfer, Me... 10 Q[5] / R-BINAM supramolecular hydrogel at 520 nm g lum It becomes -1.07×10 -3 It reaches -1.35×10 at 620nm. -3 Me 10 The Q[5] / S-BINAM supramolecular hydrogel has a strength of 1.26 × 10⁻⁶ at 520 nm. -3 At 620nm, it is 1.56×10 -3 g lum The chiral transfer is on the same order of magnitude as that of typical chiral supramolecular luminescent materials, indicating that the chiral transfer is stable and reliable.

Claims

1. A supramolecular hydrogel based on decamethyl pentaguanidinium characterized in that, The ten-methyl five-membered cucurbituril-based supramolecular hydrogel is made of ten-methyl five-membered cucurbituril and 2,2'-diamino-1,1'-binaphthyl hydrochloride.

2. A decanide-based supramolecular hydrogel according to claim 1, wherein, 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. The method for preparing a decanatrimethyl pentaguanidinium-based supramolecular hydrogel according to claim 1 or 2, characterized in that, The method comprises the following steps: (1) Me 10 Q[5] and BINAM were dissolved in water respectively and heated to dissolve, Me 10 Q[5] aqueous solution and BINAM aqueous solution; (2) Me 10 Q[5] aqueous solution and BINAM aqueous solution were mixed and heated to 75°C to obtain a transparent solution, and then ethanol was added while hot, and then slowly cooled to room temperature to form a supramolecular hydrogel.

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

5. The method for preparing a supramolecular hydrogel based on a decamethyl five-membered cucurbit ring as described in claim 3, characterized in that, The mass concentration of Me in the transparent solution is 0.38-2.43 wt%. 10 The mass concentration of Q[5] is 0.38-2.43 wt%.

6. The method for preparing a supramolecular hydrogel based on a decamethyl five-membered cucurbit ring as described in claim 3, characterized in that, The BINAM is obtained by dissolving 2,2'-diamino-1,1'-binaphthyl in hydrochloric acid and freeze-drying.

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

8. The use of the ten-methyl five-membered cucurbituril-based supramolecular hydrogel according to any one of claims 1-2 or the ten-methyl five-membered cucurbituril-based supramolecular hydrogel prepared by the method according to any one of claims 3-7 in the preparation of white light CPL materials.

9. Use according to claim 8, wherein the compound is ###0002### The white light CPL material is prepared by mixing sulfonated rhodamine B with the ten-methyl five-membered cucurbituril-based supramolecular hydrogel.

10. Use according to claim 9, wherein The mass concentration of sulfonated rhodamine B in the white light CPL material is 0.008-0.012%.

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