Intelligent chiral supramolecular helix and preparation method thereof

Abstract

The application discloses an intelligent chiral supramolecular helix and a preparation method thereof; the intelligent chiral supramolecular helix material is constructed by polyphenylene vinylene derivatives and N-hydroxysuccinimide derivatives under the driving of chemical energy carbodiimide, and obvious chiral signals exist in the ultraviolet absorption region of the polyphenylene vinylene derivatives. With the consumption of chemical energy, the chiral signals of the chiral supramolecular helix gradually weaken over time and finally disappear, and excellent intelligent behaviors of self-adaption and self-evolution are shown. When the chemical energy is repeatedly added, the chiral signals of the supramolecular helix reappear, and the chiral signals autonomously evolve over time, and the cycle process can be repeatedly carried out for multiple times.

Description

Technical Field

[0001] This invention belongs to the field of chiral supramolecular materials, specifically relating to a smart chiral supramolecular helix and its preparation method. Background Technology

[0002] Chirality is one of the fundamental characteristics of nature and an important component of living organisms, playing a unique role in maintaining their structure and function. For a long time, research on chiral supramolecular structures has been highly favored by chemists and materials scientists because chiral supramolecular structures can not only simulate chiral phenomena in biological processes, deepening our understanding of life sciences, but also promise to provide core technological support for fields such as medicine, information, and materials. This is of great significance to both socio-economic development and the advancement of basic scientific theories.

[0003] Currently, researchers have developed a large number of chiral supramolecular materials with excellent properties using molecular self-assembly technology, which have broad application prospects in fields such as data storage, chiral sensing, chiral recognition, chiral switching, and asymmetric catalysis. For example, Liu Minghua et al. from the Institute of Chemistry, Chinese Academy of Sciences, developed a chiral supramolecular gel based on glutamic acid derivatives, which can be used as a chiral recognition material (Langmuir, 2013, 29, 5435-5442); Yashima et al. from Nagoya University, Japan, developed a chiral supramolecular helical material based on polyphenylene acetylene derivatives, which can be applied to fields such as chiral resolution (Nat. Chem., 2014, 6, 429-434). However, these artificial chiral supramolecular structures still have significant differences in structural dynamics compared with the chiral structures of living organisms. Living organisms are dissipative systems in a non-thermodynamic equilibrium state, requiring continuous energy consumption (such as ATP, GTP, etc.) to maintain their complex structures and physiological functions, and possess intelligent characteristics such as autonomy and self-adaptation. In contrast, the currently reported artificial chiral supramolecular systems are in thermodynamic equilibrium. Once the system reaches equilibrium, the chirality and properties of the supramolecular material will not change over time. They lack the autonomous, dynamic, and adaptive intelligent behaviors of living organisms, which severely restricts the development and application of chiral supramolecular materials.

[0004] In order to construct intelligent chiral supramolecular materials with adaptive and autonomous evolution capabilities, this invention simulates a living organism and uses dissipative self-assembly technology with chemical energy as the energy source to prepare an intelligent chiral supramolecular helical material whose chirality can autonomously evolve over time under non-thermodynamic equilibrium conditions. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings and deficiencies of the prior art and to provide an intelligent chiral supramolecular helix and its preparation method.

[0006] This invention is achieved through the following technical solution:

[0007] This invention relates to a smart chiral supramolecular helix, formed by a non-chiral polyphenylacetylene derivative and a chiral N-hydroxysuccinimide derivative under the driving force of chemical energy carbodiimide; wherein,

[0008] The polyphenylene acetylene derivative accounts for 3% to 100% of the N-hydroxysuccinimide derivative by weight, preferably 20% to 50% of the N-hydroxysuccinimide derivative by weight.

[0009] The chemical energy of the carbodiimide is 10% to 500% by weight relative to the polyphenylene acetylene derivative, preferably 50% to 100% by weight relative to the polyphenylene acetylene derivative.

[0010] The present invention relates to a smart chiral supramolecular material in a mixed solvent of dimethyl sulfoxide and water, wherein the volume percentage of dimethyl sulfoxide is preferably 30%-50%.

[0011] The non-chiral polyphenylacetylene derivative and the chiral N-hydroxysuccinimide derivative, driven by the chemical energy of the carbodiimide derivative, generate a metastable N-hydroxysuccinimide ester, simultaneously transferring molecular chirality to the structure of the polyphenylacetylene derivative to form a chiral supramolecular helical structure. As the chemical energy is consumed, the metastable N-hydroxysuccinimide ester gradually hydrolyzes, the supramolecular helical chirality gradually weakens and eventually disappears, and the system returns to its initial state. The chirality of the supramolecular helix exhibits an autonomous evolutionary capability. This intelligent chiral supramolecular helical material can be cycled multiple times with the supply of chemical energy.

[0012] The chemical name of the carbodiimide derivative is 1-ethyl-(3-dimethylaminopropyl)carbodiimide, N,N'-diisopropylcarbodiimide or dicyclohexylcarbodiimide, preferably 1-ethyl-(3-dimethylaminopropyl)carbodiimide.

[0013] The chemical name of the aforementioned non-chiral polyphenylacetylene derivative is poly-(4-ethyl phosphate phenyl)-acetylene, with a number-average molecular weight of 100,000–230,000 g / mol, and its chemical structure is as follows:

[0014]

[0015] The chiral N-hydroxysuccinimide derivative has the following general formula:

[0016]

[0017] In the formula, R is -CH2C6H5; -CH3; -OCH3. The three N-hydroxysuccinimide derivatives with different substituents are abbreviated as Benzyl-NHS, Methyl-NHS, and Methoxy-NHS, respectively, and their chiral configurations can be (R) or (S).

[0018] The method for preparing the intelligent chiral supramolecular helix of the present invention is as follows:

[0019] (1) Weigh an appropriate amount of polyphenylacetylene derivative and dissolve it in dimethyl sulfoxide to prepare a polyphenylacetylene derivative solution (the concentration of the polyphenylacetylene derivative is 0.5 mg / mL to 5.0 mg / mL) for later use;

[0020] (2) Weigh a certain amount of chiral N-hydroxysuccinimide derivative and dissolve it in deionized water to obtain an N-hydroxysuccinimide derivative solution (concentration of 0.5 mg / mL to 20.0 mg / mL) for later use;

[0021] (3). The solutions obtained in steps (1) and (2) are mixed in a certain ratio (3:7 to 5:5) to obtain a water-dimethyl sulfoxide mixed solution of polyphenylacetylene derivative and chiral N-hydroxysuccinimide derivative (preferably the volume ratio of dimethyl sulfoxide is 30% to 50%) (preferably the concentration of polyphenylacetylene derivative is 0.5 mg / mL to 2.0 mg / mL, and the weight of polyphenylacetylene derivative relative to N-hydroxysuccinimide derivative is 20% to 50%).

[0022] (4) Weigh a certain amount (equivalent to 0.1 to 5 equivalents of poly-(4-ethyl phosphate phenyl)-acetylene) of carbodiimide derivative (preferably 1-ethyl-(3-dimethylaminopropyl)carbodiimide) and add it to the mixed solution obtained in step (3) and mix evenly (preferably the weight of the carbodiimide derivative relative to the polyphenylacetylene derivative is 50% to 100%) to obtain a smart chiral supramolecular helical material.

[0023] Compared with the prior art, the present invention has the following advantages and effects:

[0024] Characterized by circular dichroism spectroscopy, the intelligent chiral supramolecular material of this invention exhibits a distinct chiral signal at the ultraviolet absorption region (300–500 nm) of the polyphenylene acetylene derivative. Driven by the chemical energy of carbodiimide, this supramolecular material forms a chiral helical structure, and as the chemical energy is consumed, the chiral signal of the supramolecular material autonomously weakens over time and returns to its initial state. Subsequently, by repeatedly adding chemical energy to the system, the chiral signal reappears and autonomously evolves over time. This cyclic process can be repeated multiple times.

[0025] Chirality is closely related to life sciences and materials science. Currently, artificial chiral supramolecular systems differ significantly from living systems in terms of structural dynamics, particularly lacking the autonomy, dynamic adaptation, and spatiotemporal controllability characteristic of living organisms, which severely restricts the development of chiral science. This invention, simulating a living organism, utilizes a dissipative self-assembly strategy, driven by chemical energy, to form transient chiral assemblies. The chirality of these assemblies autonomously weakens and eventually disappears as chemical energy is consumed, restoring the system to its initial state. This process can be repeated multiple times with repeated energy supply. This transient chiral supramolecular material system provides a foundation and platform for researching novel biomimetic chiral materials that are autonomous, self-healing, and adaptive, and has broad application prospects in fields such as artificial intelligence, intelligent manufacturing, and biomedicine. Attached Figure Description

[0026] Figure 1 This is an example of the change in chiral signal over time of a chiral supramolecular helix after the addition of chemical energy in Example 1 of the present invention.

[0027] Figure 2 The chiral signal intensity at 367 nm of the chiral supramolecular helix in Example 1 of this invention changes over time.

[0028] Figure 3 The chiral signal of the chiral supramolecular helix in Example 2 of this invention changes over time after chemical energy is added.

[0029] Figure 4 The chiral signal intensity at 367 nm of the chiral supramolecular helix in Example 2 of this invention changes over time.

[0030] In the attached figures, a represents the chiral signal of the supramolecular helix after 1 minute of adding chemical energy 1-ethyl-(3-dimethylaminopropyl)carbodiimide; b represents the chiral signal of the supramolecular helix after the chemical energy 1-ethyl-(3-dimethylaminopropyl)carbodiimide has been completely consumed. Detailed Implementation

[0031] The present invention will now be described in further detail with reference to specific embodiments.

[0032] Example 1:

[0033] Weigh 1 mg of poly-(4-ethyl phosphate phenyl)-acetylene (molecular weight 10). 5A 3 mg / mL poly-(4-ethyl phosphate phenyl)-acetylene solution was prepared by dissolving (R)-Benzyl-NHS in 0.3 mL of dimethyl sulfoxide. Simultaneously, 3.5 mg of (R)-Benzyl-NHS was dissolved in 0.7 mL of deionized water to obtain a 5 mg / mL (R)-Benzyl-NHS solution. Then, the two solutions were mixed thoroughly, and 1 mg of 1-ethyl-(3-dimethylaminopropyl)carbodiimide was added to obtain a smart chiral supramolecular helical material with autonomous evolution capabilities.

[0034] The chiral signal and its autonomous evolution ability over time of the obtained transient chiral supramolecular material were tested using circular dichroism spectroscopy (Applied Photophysics Chirascan, UK). Upon addition of 1-ethyl-(3-dimethylaminopropyl)carbodiimide, a significant chiral signal appeared in the UV absorption region (300–500 nm) of poly(4-ethyl phosphate phenyl)-acetylene, indicating the formation of a chiral supramolecular helical structure. As time passed, the chemical energy in the system was gradually consumed, and the chiral signal of the supramolecular helix gradually weakened and eventually disappeared, indicating that the chiral supramolecular helical structure possesses autonomous evolution ability. Subsequently, 1-ethyl-(3-dimethylaminopropyl)carbodiimide was added to the system again. Circular dichroism spectroscopy revealed that a chiral signal reappeared in the UV absorption region of poly(4-ethyl phosphate phenyl)-acetylene, and the signal was identical to the previous one, gradually weakening and eventually disappearing over time. This process could be repeated multiple times. This indicates that the chirality of this supramolecular helix possesses adaptive capabilities, enabling it to evolve autonomously based on the chemical energy of its environment. Figure 1 The graph shows the change of the CD signal of the supramolecular helix over time under the drive of chemical energy. Figure 2 The graph shows the change in CD signal intensity at 367 nm over time for this supramolecular helix driven by chemical energy.

[0035] Example 2:

[0036] Weigh 1 mg of poly-(4-ethyl phosphate phenyl)-acetylene (molecular weight 10). 5 0.6 mg of (R)-Methyl-NHS was dissolved in 1 mL of a mixed solution of deionized water and dimethyl sulfoxide (dimethyl sulfoxide volume percentage 30%). After poly-(4-ethyl phosphate phenyl)-acetylene and (R)-Methyl-NHS were completely dissolved, 1 mg of 1-ethyl-(3-dimethylaminopropyl)carbodiimide was added to the mixed solution to prepare a smart chiral supramolecular helical material.

[0037] The obtained intelligent chiral supramolecular material was tested for its chiral signal and its autonomous evolution ability over time using circular dichroism spectroscopy (Applied Photophysics Chirascan, UK). Upon addition of 1-ethyl-(3-dimethylaminopropyl)carbodiimide, a significant chiral signal appeared in the UV absorption region (300–500 nm) of poly(4-ethyl phosphate phenyl)-acetylene, indicating the formation of a chiral supramolecular helical structure. As time passed, the chemical energy in the system was gradually consumed, and the chiral signal of the supramolecular helix gradually weakened and eventually disappeared, indicating that the chiral supramolecular helical structure possesses autonomous evolution ability. Subsequently, 1-ethyl-(3-dimethylaminopropyl)carbodiimide was added to the system again. Circular dichroism spectroscopy revealed that the system again exhibited a chiral signal in the UV absorption region of poly(4-ethyl phosphate phenyl)-acetylene, and the signal was identical to the previous one, gradually weakening and eventually disappearing over time. This process could be repeated multiple times, indicating that the chiral supramolecular helical structure possesses autonomous evolution ability. Figure 3 The graph shows the change of the CD signal of the supramolecular helix over time under the drive of chemical energy. Figure 4 The graph shows the change in CD signal intensity at 367 nm over time for this supramolecular helix driven by chemical energy.

[0038] As described above, the present invention can be implemented well.

[0039] The implementation of the present invention is not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A smart chiral supramolecular helicoid, characterized in that, The supramolecular helix is constructed by a non-chiral polyphenylacetylene derivative and a chiral N-hydroxysuccinimide derivative under the driving of chemical energy carbodiimide; The non-chiral polyphenylacetylene derivative is poly-(4-phosphoethylphenyl)-acetylene with a number average molecular weight of 100000-2300000, and has the following chemical structure: The chiral N-hydroxysuccinimide derivative has the following general formula: In the formula, R is -CH2C6H5, -CH3 or -OCH3, and the chiral configuration can be (R) or (S).

2. The smart chiral supramolecular helicate according to claim 1, wherein, The weight of the polyphenylacetylene derivative relative to the N-hydroxysuccinimide derivative is 3%-100%.

3. The smart chiral supramolecular helicate of claim 2, wherein, The weight of the chemical energy carbodiimide relative to the polyphenylacetylene derivative is 10%-500%.

4. The smart chiral supramolecular helicate of claim 3, wherein, The supramolecular helix structure is in a mixed solvent of dimethyl sulfoxide and water, wherein the volume ratio of dimethyl sulfoxide is 30%-50%.

5. The smart chiral supramolecular helicate of claim 4, wherein, The chemical energy is 1-ethyl-(3-dimethylaminopropyl) carbodiimide, N,N'-diisopropyl carbodiimide or dicyclohexyl carbodiimide.

6. The smart chiral supramolecular helicate of claim 5, wherein, The supramolecular helix generates a chiral signal at 300-500 nm under the driving of the chemical energy, and the intensity of the chiral signal gradually decreases and finally disappears with the consumption of the chemical energy; then, when the chemical energy is supplied to the system again, the chiral signal appears again and evolves autonomously, and this intelligent autonomous evolution capability can be repeated for multiple times.

7. A process for the preparation of the smart chiral supramolecular helicoidal structures according to any one of claims 1 to 6, characterized in that The method comprises the following steps: Step one: weigh the poly-(4-phosphoethylphenyl)-acetylene, dissolve it in dimethyl sulfoxide to prepare a poly-(4-phosphoethylphenyl)-acetylene solution, wherein the concentration of the poly-(4-phosphoethylphenyl)-acetylene is 0.5 mg / mL-5.0 mg / mL; Step two: weigh the chiral N-hydroxysuccinimide derivative (R)-Benzyl-NHS, dissolve it in deionized water to obtain a (R)-Benzyl-NHS solution for use, wherein the concentration of the (R)-Benzyl-NHS is 0.5 mg / mL-20.0 mg / mL; Step three: mix the solutions obtained in steps one and two according to a proportion to obtain a water-dimethyl sulfoxide mixed solution of the polyphenylacetylene derivative and the chiral N-hydroxysuccinimide derivative, wherein the volume ratio of dimethyl sulfoxide is 30%-50%; Step four: add chemical energy carbodiimide to the mixed solution obtained in step three and mix uniformly to obtain an intelligent chiral supramolecular helix with autonomous evolution capability.

8. The method for preparing the intelligent chiral supramolecular helix according to claim 7, characterized in that, In step three, the mixing according to a proportion is mixing according to a proportion of 3:7-5:

5.

9. The method for preparing the intelligent chiral supramolecular helix according to claim 8, characterized in that, In step four, the amount of the chemical energy carbodiimide added is 0.1-5 times the amount of the poly-(4-phosphoethylphenyl)-acetylene.

Images