Preparation method of cucurbituril-based rare earth supermolecular hydrogel

Abstract

The application discloses a preparation method of cucurbituril-based rare earth supramolecular hydrogel, and belongs to the technical field of chemical synthesis. The method utilizes the synergistic effect of 3-amino 2,7-naphthalene disulfonic acid monosodium salt organic ligand and rare earth metal ions, and designs and synthesizes 13 kinds of supramolecular hydrogels with similar properties. The preparation method of the cucurbituril-based rare earth supramolecular hydrogel has the characteristics of simple operation, low energy consumption and short synthesis time. By using the organic ligand 3-amino 2,7-naphthalene disulfonic acid monosodium salt, the ordered arrangement of the five-membered cucurbituril is promoted, the system plays a double role of 'counter anion' and 'bridging', and the amino group in the ligand points to the straight channel, so that a large number of water molecules are connected in the one-dimensional channel through the hydrogen bond effect between the amino groups on the 3-amino 2,7-naphthalene disulfonic acid monosodium salt, and a final gel structure is formed. Due to the existence of non-covalent connection, the foundation is laid for the application in the aspects of stimulus response and self-healing ability of substances.

Description

Technical Field

[0001] This invention belongs to the field of chemical synthesis technology, specifically relating to a method for preparing a class of cucurbitacin rare earth supramolecular hydrogels. Background Technology

[0002] Many researchers both domestically and internationally have reported various cucurbitacinized hydrogels in different open-access journals. However, the synthesis methods for these hydrogel materials are often complex or have long synthesis cycles. To address these issues, a method for preparing cucurbitacinized rare-earth supramolecular hydrogels is proposed. Summary of the Invention

[0003] In view of the shortcomings of the prior art, the purpose of this invention is to provide a method for preparing a class of cucurbitacin rare earth supramolecular hydrogels.

[0004] The objective of this invention can be achieved through the following technical solutions:

[0005] A method for preparing a class of cucurbitacin-based rare-earth supramolecular hydrogels includes the following steps:

[0006] Weigh the five-membered cucurbitacin or cucurbita[5], the monosodium salt of 3,-amino-2,7-naphthalenedisulfonic acid and the rare earth metal salt in a molar ratio of 1:1-2:8-10 respectively;

[0007] Five-membered cucurbitacin or cucurbituril[5] and rare earth metal salts were respectively added to water to obtain five-membered cucurbitacin or cucurbituril[5] solutions and rare earth metal salt solutions, and then heated and stirred.

[0008] 3,-Amino-2,7-naphthalenedisulfonic acid monosodium salt was added to water and stirred to obtain a 3,-amino-2,7-naphthalenedisulfonic acid monosodium salt solution;

[0009] After mixing the three solutions and allowing them to stand, a hydrogel is obtained.

[0010] Furthermore, the solution preparation process involves heating and stirring at a temperature of 50℃ to 80℃ to prepare a solution of 10 mg / mL. -1 A solution of quinone cucurbitacin or cucurbita[5] and 0.1 mol·L -1 Rare earth metal solutions.

[0011] Furthermore, the rare earth metal salt is a rare earth metal hydrochloride or nitrate.

[0012] Furthermore, the 3,6-amino-2,7-naphthalenedisulfonic acid monosodium solution has a concentration of 3.6 mg / mL. -1 A solution of 3,-amino-2,7-naphthalenedisulfonic acid monosodium salt.

[0013] Furthermore, all three solutions must be clear and transparent before mixing, and should be mixed evenly at room temperature and allowed to stand for 0.5-10 minutes.

[0014] The beneficial effects of this invention are:

[0015] This invention discloses a method for preparing a class of cucurbitacin-based rare-earth supramolecular hydrogels. Utilizing the synergistic effect of a monosodium 3,-amino-2,7-naphthalenedisulfonic acid ligand and rare-earth metal ions, 13 supramolecular hydrogels with similar properties (such as...) were designed and synthesized. Figure 1 );

[0016] The preparation method provided by this invention features simple operation, low energy consumption, and short synthesis time. By using the organic ligand 3,-amino-2,7-naphthalenedisulfonic acid monosodium salt (ANDSO), not only is the ordered arrangement of the five-membered cucurbit rings promoted, which act as both "counterion anions" and "bridging" in the system, but the amino groups in the ligand also point towards the straight-through channels. This allows a large number of water molecules to be connected to the one-dimensional channels through hydrogen bonding with the amino groups on the 3,-amino-2,7-naphthalenedisulfonic acid monosodium salt, forming the final gel structure. Figure 2 );

[0017] Throughout the structure, the amino groups in the ANDSO ligand point towards the through-channels, allowing a large number of water molecules to be connected to the one-dimensional channels via hydrogen bonds with the amino groups on the ANDSO ligands. These non-covalent interactions promote hydrogel formation. Furthermore, it is precisely the existence of these non-covalent interactions that lays the foundation for its applications in areas such as stimulus response and self-healing capabilities. Figure 3-9 ). Attached Figure Description

[0018] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, for those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0019] Figure 1 This is a photograph of a type of cucurbitacin rare earth supramolecular hydrogel of the present invention under fluorescent light;

[0020] Figure 2 This is a crystal structure diagram of a cucurbitacin rare earth supramolecular hydrogel obtained in Example 3 of the present invention;

[0021] Figure 3 This is the infrared spectrum of a cucurbitacin rare earth supramolecular hydrogel obtained in Example 3 of the present invention;

[0022] Figure 4 This is a fluorescence spectrum of a cucurbitacin rare earth supramolecular hydrogel obtained in Example 3 of the present invention before and after repair;

[0023] Figure 5This is a SEM image of a cucurbitacin rare earth supramolecular hydrogel freeze-dried (left) and its crystal (right) obtained in Example 3 of the present invention;

[0024] Figure 6 This is the stimulation response result of a cucurbitacin rare earth supramolecular hydrogel obtained in Example 3 of the present invention at different temperatures; the gel was destroyed at 90°C.

[0025] Figure 7 This is the stimulation response result of a cucurbitacin rare earth supramolecular hydrogel obtained in Example 3 of the present invention after the addition of various anions. The gel was destroyed after the addition of some anions.

[0026] Figure 8 This is the stimulation response result of a cucurbitacin rare earth supramolecular hydrogel obtained in Example 3 of the present invention after the addition of various cations; the gel was destroyed after the addition of some cations.

[0027] Figure 9 The results of the stimulation response of the cucurbitacin rare earth supramolecular hydrogel obtained in Example 3 of this invention after adding various organic solvents show that the gel was destroyed after adding some organic solvents.

[0028] Figure 10 This is the structural formula of the five-membered cucurbit ring (right) and monosodium 3,-amino-2,7-naphthalenedisulfonic acid (ANDSO) (left) of the present invention. Detailed Implementation

[0029] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] A method for preparing a class of cucurbit-based rare-earth supramolecular hydrogels, wherein the structural formulas of the five-membered cucurbit ring (right) and monosodium 3,-amino-2,7-naphthalenedisulfonic acid (ANDSO) (left) are shown in the figure. Figure 10 As shown.

[0031] Example 1: Preparation of cucurbitacin-based rare earth supramolecular hydrogels (five-membered cucurbitacin or cucurbituril[5]-ANDSO-Ce3+)

[0032] Weigh the five-membered cucurbitacin or cucurbituril[5], monosodium salt of 3,-amino-2,7-naphthalenedisulfonic acid and cerium nitrate in a molar ratio of 1:1 to 2:8 to 10 respectively; heat the weighed five-membered cucurbitacin or cucurbituril[5], monosodium salt of 3,-amino-2,7-naphthalenedisulfonic acid and cerium nitrate with an appropriate amount of water and stir with a strong magnetic force; after all three have become clear and transparent solutions, quickly mix them evenly at room temperature and let them stand for one minute to obtain cucurbitacin-based rare earth supramolecular hydrogel.

[0033] Example 2: Cucurbitacin-based rare earth supramolecular hydrogel (five-membered cucurbitacin or cucurbituril[5]-ANDSO-Pr) 3+ Preparation of )

[0034] Weigh the five-membered cucurbitacin or cucurbituril[5], monosodium salt of 3,-amino-2,7-naphthalenedisulfonic acid and praseodymium nitrate in a molar ratio of 1:1 to 2:8 to 10 respectively; heat the weighed five-membered cucurbitacin or cucurbituril[5], monosodium salt of 3,-amino-2,7-naphthalenedisulfonic acid and praseodymium nitrate with an appropriate amount of water and stir with a strong magnetic force; after all three have become clear and transparent solutions, quickly mix them evenly at room temperature and let them stand for one minute to obtain cucurbitacin-based rare earth supramolecular hydrogel.

[0035] Example 3: Cucurbitacin-based rare earth supramolecular hydrogel (five-membered cucurbitacin or cucurbituril[5]-ANDSO-Nd) 3+ Preparation of )

[0036] Weigh the five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and neodymium nitrate in a molar ratio of 1:1 to 2:8 to 10 respectively; heat the weighed five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and neodymium nitrate with an appropriate amount of water and stir with a strong magnetic force; after all three have become clear and transparent solutions, quickly mix them evenly at room temperature and let them stand for one minute to obtain cucurbitacin-based rare earth supramolecular hydrogel.

[0037] Example 4: Cucurbitacin-based rare earth supramolecular hydrogel (five-membered cucurbitacin or cucurbituril[5]-ANDSO-Sm) 3+ Preparation of )

[0038] Weigh the five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and samarium nitrate in a molar ratio of 1:1 to 2:8 to 10 respectively; heat the weighed five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and samarium nitrate with an appropriate amount of water and stir with a strong magnetic force; after all three have become clear and transparent solutions, quickly mix them evenly at room temperature and let them stand for one minute to obtain cucurbitacin-based rare earth supramolecular hydrogel.

[0039] Example 5: Cucurbitacin-based rare earth supramolecular hydrogel (five-membered cucurbitacin or cucurbituril[5]-ANDSO-Eu) 3+Preparation of )

[0040] Weigh the five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and europium nitrate in a molar ratio of 1:1 to 2:8 to 10 respectively; heat the weighed five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and europium nitrate with an appropriate amount of water and stir with a strong magnetic force; after all three have become clear and transparent solutions, quickly mix them evenly at room temperature and let them stand for one minute to obtain cucurbitacin-based rare earth supramolecular hydrogel.

[0041] Example 6: Cucurbitacin-based rare earth supramolecular hydrogel (five-membered cucurbitacin or cucurbituril[5]-ANDSO-Gd) 3+ Preparation of )

[0042] Weigh the five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and gadolinium nitrate in a molar ratio of 1:1 to 2:8 to 10 respectively; heat the weighed five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and gadolinium nitrate with an appropriate amount of water and stir with a strong magnetic force; after all three have become clear and transparent solutions, quickly mix them evenly at room temperature and let them stand for one minute to obtain cucurbitacin-based rare earth supramolecular hydrogel.

[0043] Example 7: Cucurbitacin-based rare earth supramolecular hydrogel (five-membered cucurbitacin or cucurbituril[5]-ANDSO-Tb) 3+ Preparation of )

[0044] Weigh the five-membered cucurbitacin or cucurbituril[5], monosodium salt of 3,-amino-2,7-naphthalenedisulfonic acid and terbium nitrate in a molar ratio of 1:1 to 2:8 to 10 respectively; heat the weighed five-membered cucurbitacin or cucurbituril[5], monosodium salt of 3,-amino-2,7-naphthalenedisulfonic acid and terbium nitrate with an appropriate amount of water and stir with a strong magnetic force; after all three have become clear and transparent solutions, quickly mix them evenly at room temperature and let them stand for one minute to obtain cucurbitacin-based rare earth supramolecular hydrogel.

[0045] Example 8: Cucurbitacin-based rare earth supramolecular hydrogel (five-membered cucurbitacin or cucurbituril[5]-ANDSO-Dy 3+ Preparation of )

[0046] Weigh the five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and dysprosium nitrate in a molar ratio of 1:1 to 2:8 to 10 respectively; heat the weighed five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and dysprosium nitrate with an appropriate amount of water and stir with a strong magnetic force; after all three have become clear and transparent solutions, quickly mix them evenly at room temperature and let them stand for one minute to obtain cucurbitacin-based rare earth supramolecular hydrogel.

[0047] Example 9: Cucurbitacin-based rare earth supramolecular hydrogel (five-membered cucurbitacin or cucurbituril[5]-ANDSO-Ho) 3+ Preparation of )

[0048] Weigh the five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and holmium nitrate in a molar ratio of 1:1 to 2:8 to 10 respectively; heat the weighed five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and holmium nitrate with an appropriate amount of water and stir with a strong magnetic force; after all three have become clear and transparent solutions, quickly mix them evenly at room temperature and let them stand for one minute to obtain cucurbitacin-based rare earth supramolecular hydrogel.

[0049] Example 10: Cucurbitacin-based rare earth supramolecular hydrogel (five-membered cucurbitacin or cucurbituril[5]-ANDSO-Er) 3+ Preparation of )

[0050] Weigh the five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and erbium nitrate in a molar ratio of 1:1 to 2:8 to 10 respectively; heat the weighed five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and erbium nitrate with an appropriate amount of water and stir with a strong magnetic force; after all three have become clear and transparent solutions, quickly mix them evenly at room temperature and let them stand for one minute to obtain cucurbitacin-based rare earth supramolecular hydrogel.

[0051] Example 11: Cucurbitacin-based rare earth supramolecular hydrogel (five-membered cucurbitacin or cucurbituril[5]-ANDSO-Tm) 3+ Preparation of )

[0052] Weigh the five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and thulium nitrate in a molar ratio of 1:1 to 2:8 to 10 respectively; heat the weighed five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and thulium nitrate with an appropriate amount of water and stir with a strong magnetic force; after all three have become clear and transparent solutions, quickly mix them evenly at room temperature and let them stand for one minute to obtain cucurbitacin-based rare earth supramolecular hydrogel.

[0053] Example 12: Cucurbitacin-based rare earth supramolecular hydrogel (five-membered cucurbitacin or cucurbituril[5]-ANDSO-Yb) 3+ Preparation of )

[0054] Weigh the five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and ytterbium nitrate in a molar ratio of 1:1 to 2:8 to 10 respectively; heat the weighed five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and ytterbium nitrate with an appropriate amount of water and stir with a strong magnetic force; after all three have become clear and transparent solutions, quickly mix them evenly at room temperature and let them stand for one minute to obtain cucurbitacin-based rare earth supramolecular hydrogel.

[0055] Example 13: Cucurbitacin-based rare earth supramolecular hydrogel (five-membered cucurbitacin or cucurbituril[5]-ANDSO-Lu 3+ Preparation of )

[0056] Weigh the five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and lutetium nitrate in a molar ratio of 1:1 to 2:8 to 10 respectively; heat the weighed five-membered cucurbitacin or cucurbituril[5], monosodium 3,-amino-2,7-naphthalenedisulfonic acid and lutetium nitrate with an appropriate amount of water and stir with a strong magnetic force; after all three have become clear and transparent solutions, quickly mix them evenly at room temperature and let them stand for one minute to obtain cucurbitacin-based rare earth supramolecular hydrogel.

[0057] This invention features simple operation, low energy consumption, and short time consumption. By using the organic ligand 3,-amino-2,7-naphthalenedisulfonic acid monosodium salt, it not only promotes the orderly arrangement of the five-membered cucurbit rings but also acts as both a "counter-anion" and "bridge" in the system. Furthermore, the amino groups in the ligand point towards the straight-through channels, allowing a large number of water molecules to be connected to the one-dimensional channels through hydrogen bonding with the amino groups on the 3,-amino-2,7-naphthalenedisulfonic acid monosodium salt, forming the final gel structure. The presence of non-covalent connections lays the foundation for its application in areas such as stimulus response and self-healing capabilities.

[0058] Figure 2 The cucurbitacin-based rare earth supramolecular hydrogel (Nd) of Example 3 3+ Crystal structure diagram of ), where (a) five-membered cucurbit ring-Nd 3+ (a) One-dimensional supramolecular chain; (b) Self-inductive interaction between a five-membered cucurbit ring on a one-dimensional supramolecular chain and a five-membered cucurbit ring on an adjacent one-dimensional supramolecular chain; (c) Two-dimensional planar structure formed by self-induction of a one-dimensional supramolecular chain; (d) Weak interaction between a five-membered cucurbit ring molecule and an ANDSO ligand; (e) Three-dimensional cucurbit ring-based rare earth supramolecular structure with one-dimensional channels.

[0059] Figure 3 The cucurbitacin-based rare earth supramolecular hydrogel (Nd) of Example 3 3+ Infrared spectrum of ANDSO ligand (2626 cm⁻¹) -1The characteristic functional group vibration of -OH in the sulfonic acid group was observed at 2940 cm⁻¹, but it was almost annihilated in the gel; similarly, in the infrared spectrum of Q[5], the characteristic functional group vibration of -OH in the sulfonic acid group was observed at 2940 cm⁻¹. -1 and 3000cm -1 Vibrations of characteristic functional groups, including the bridging methylene group and the methine group at the equatorial plane, were observed in the cucurbit ring, but their intensity decreased in the gel. This indicates the presence of hydrogen bonding or CH…π interactions between the sulfonic acid groups in the ANDSO ligand and the outer wall of the cucurbit ring, promoting the formation of the final gel network.

[0060] Figure 4 Example 3: Cucurbitacinized Rare Earth Supramolecular Hydrogel (Nd) 3+ Fluorescence spectra before and after repair. (Under vigorous shaking, the hydrogel transforms from a gel to a sol. Heating the sol to boiling until clear and then cooling it back to a gel state results in minimal or even increased fluorescence intensity after repair, indicating that the hydrogel possesses strong repair properties.)

[0061] Figure 5 Example 3: Cucurbitacinized Rare Earth Supramolecular Hydrogel (Nd) 3+ SEM images of the freeze-dried product (left) and its crystal (right).

[0062] Figure 6 Example 3: Cucurbitacinized Rare Earth Supramolecular Hydrogel (Nd) 3+ The gel was destroyed at 90℃ (at a high temperature of 90℃, the phase of the gel changed, beginning to transform from a gel to a sol, but the fluorescence intensity remained basically unchanged. This indicates that the gel can withstand high temperatures below 90℃ and has good thermal stability).

[0063] Figure 7 Example 3: Cucurbitacinized Rare Earth Supramolecular Hydrogel (Nd) 3+ The gel was disrupted after the addition of some anions (under certain conditions, the five-membered cucurbit ring solution exhibits aggregation-induced emission (AIE). Therefore, when the above-mentioned anions are introduced, they interact with the outer wall of the five-membered cucurbit ring, leading to a change in the hydrogen bond network in the gel, which ultimately causes a change in the gel phase).

[0064] Figure 8 Example 3: Cucurbitacinized Rare Earth Supramolecular Hydrogel (Nd) 3+ The gel was disrupted after the addition of some cations (the introduction of the aforementioned metal ions may affect Nd). 3+ The coordination ability of Sr or its direct participation in coordination leads to changes in the gel phase, in which Sr 2+ Ba 2+ Pb 2+ (This promoted the enhancement of gel fluorescence intensity).

[0065] Figure 9Example 3: Cucurbitacinized Rare Earth Supramolecular Hydrogel (Nd) 3+ The gel was disrupted after the addition of some organic solvents (benzene and aniline can quench the fluorescence intensity of the gel, while acetonitrile and n-hexane have little effect on the fluorescence intensity).

[0066] Table 1 shows a cucurbitacin-based rare earth supramolecular hydrogel (Nd) obtained in Example 3. 3+ Crystal structure parameter table

[0067]

[0068] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0069] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. A method for preparing a cucurbitacin-based rare earth supramolecular hydrogel, characterized in that, Includes the following steps: Weigh the five-membered cucurbitacin, monosodium salt of 3-amino-2,7-naphthalenedisulfonic acid and rare earth metal salt separately in a molar ratio of 1:1 to 2:8 to 10. Five-membered cucurbitacin and rare earth metal salt were respectively added to water to obtain five-membered cucurbitacin solution and rare earth metal salt solution, and then heated and stirred. A solution of 3-amino-2,7-naphthalenedisulfonic acid monosodium salt was obtained by adding water and stirring. After mixing the three solutions and allowing them to stand, a hydrogel is obtained.

2. The method for preparing a cucurbitacin-based rare earth supramolecular hydrogel according to claim 1, characterized in that, The heating temperature is 50℃~80℃, and the pentagonal cucurbitacin solution and rare earth metal salt solution are respectively 10 and 0.1 .

3. The method for preparing a cucurbitacin-based rare earth supramolecular hydrogel according to claim 1, characterized in that, The rare earth metal salt is a hydrochloride or nitrate of a rare earth metal.

4. The method for preparing a cucurbitacin-based rare earth supramolecular hydrogel according to claim 1, characterized in that, The 3-amino-2,7-naphthalenedisulfonic acid monosodium salt solution has a concentration of 3.6%. .

5. The method for preparing a cucurbitacin-based rare earth supramolecular hydrogel according to claim 1, characterized in that, The three solutions must be clear and transparent before mixing. They should be mixed evenly at room temperature and allowed to stand for 0.5-10 minutes.

6. The cucurbitacin-based rare earth supramolecular hydrogel prepared by the preparation method according to any one of claims 1-5.

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