Preparation method of chiral dendronized diacetylene acid molecule and supramolecular chiral assembly of chiral dendronized diacetylene acid molecule

Abstract

The invention discloses a preparation method of a chiral dendronized diacetylene acid molecule and a supramolecular chiral assembly of the chiral dendronized diacetylene acid molecule, and relates to the field of intelligent chiral materials.The preparation method comprises the steps that firstly, tree-shaped alkoxy ether is combined with PCDA through lysine, the tree-shaped alkoxy ether serves as a hydrophilic element, lysine serves as a chiral source and can provide a large number of hydrogen bonds, the PCDA serves as a hydrophobic element, and the supermolecular chiral assembly of the chiral dendronized diacetylene acid molecule is obtained; chiral dendronized diacetylene acid molecules are designed and synthesized; then, supermolecule chiral assembly is carried out through driving of non-covalent interaction, and supermolecule chiral assembly is regulated and controlled through temperature and light; furthermore, the supramolecular chiral assembly is subjected to optical topological polymerization reaction to prepare the valence-donating chiral polymer. The invention opens up a new way for creating a novel intelligent chiral nano material with a special structure and excellent characteristics.

Description

Technical Field

[0001] This invention relates to the field of intelligent chiral materials, specifically a method for preparing chiral dendritic diaethynic acid molecules and their supramolecular chiral assemblies. Background Technology

[0002] Supramolecular chiral assembly is generally driven by non-covalent interactions such as hydrophilic-hydrophobic interactions, hydrogen bonds, and π-π stacking. It exhibits both order and dynamic characteristics, along with significant abilities in stimulus response, environmental adaptation, and chiral amplification. Based on highly oriented and reversible non-covalent interactions, researchers have designed a large number of interesting chiral assembly systems. These systems can achieve flexible and precise control of chiral assembly by changing assembly conditions or applying external stimuli, opening new avenues for creating novel intelligent chiral nanomaterials with unique structures and superior properties.

[0003] Furthermore, by combining dendritic alkoxy ethers with specific topological structures with chiral lysine residues and introducing photocurable crosslinkable diacetylene, a series of intelligent responsive dendritic chiral molecules can be constructed for supramolecular chiral assembly. This allows for reversible regulation of the supramolecular chirality of the assembled molecules through external stimuli. In-depth and systematic research on the regulation of supramolecular chirality by external stimuli helps to provide a more comprehensive understanding of the role of chirality in the natural evolutionary process and provides guidance for the application of chirality in physics, chemistry, biology, materials science, and other fields.

[0004] In fact, many studies have reported on the achievement of supramolecular chiral assembly by introducing a diacetylene moiety, and the assemblies can undergo phototopological polymerization. However, most diacetylene systems do not have stimulus responsiveness and cannot be regulated by the external environment. Therefore, the flexible and reversible regulation of supramolecular chiral assembly by external stimuli remains a challenge. Summary of the Invention

[0005] To address the problems of the prior art, the present invention aims to overcome the shortcomings of the existing technology and provide a method for preparing chiral dendritic diaethynic acid molecules and their supramolecular chiral assemblies. By combining characteristic building blocks together, a stimuli-responsive supramolecular assembly is obtained. Temperature and light can dynamically control the supramolecular chirality, and under light irradiation, the supramolecular chiral assembly can be transformed into a covalent chiral polymer.

[0006] One of the objectives of this invention is to provide a chiral dendritic diaethynic acid molecule, comprising a dendritic alkoxy ether moiety with a characteristic topological structure as a hydrophilic moiety, a lysine moiety with multiple hydrogen bond sites as a chiral source, and a photocrosslinkable diaethynic acid moiety as a hydrophobic moiety.

[0007] Preferably, the structural formula of the chiral dendritic diacetynyl acid molecule is:

[0008]

[0009] in,

[0010]

[0011] Preferably, the chiral dendritic diacetynyl acid molecule is stimuli-responsive.

[0012] The second objective of this invention is to provide a method for preparing chiral dendritic diacetynyl acid molecules, specifically:

[0013] The reactants include:

[0014] Compound PCDA-Lys-G2-OL and dendritic polyamide amine-carboxyl-linked block copolymer,

[0015] The structural formula of compound PCDA-Lys-G2-OL is as follows:

[0016]

[0017] Preferably, the dendritic polyamide amine-carboxyl block copolymer is G1-COOH or G2-COOH.

[0018] Preferably, the reactants are dissolved in DCM, DMAP and EDC·HCl are added, and the reaction is carried out under a protective atmosphere and at 0°C to prepare the product.

[0019] The third objective of this invention is to provide a method for preparing supramolecular chiral assemblies using the above-mentioned chiral dendritic diacetynyl acid molecules, specifically as follows:

[0020] Chiral dendritic diaethynic acid molecules were mixed with acetone to prepare an assembly solution. After the acetone evaporated, the supramolecular chiral assembly was obtained.

[0021] Preferably, the concentration of the assembly solution is 5 mg / mL.

[0022] Preferably, the chirality of the supramolecular chiral assembly is temperature-reversibly tunable.

[0023] The fourth objective of this invention is to provide a method for preparing covalent chiral polymers using the above-mentioned supramolecular chiral assemblies, specifically:

[0024] The above supramolecular chiral assembly was irradiated with light to obtain the covalent chiral polymer.

[0025] Compared with the prior art, the beneficial effects of the present invention are:

[0026] (1) This invention provides a method for preparing a chiral dendritic diaethynic acid molecule with stimulus responsiveness. Through reasonable molecular structure design, a dendritic alkoxy ether is combined with PCDA via lysine. The dendritic alkoxy ether is a hydrophilic unit, PCDA is a hydrophobic unit, lysine is a chiral source, and provides a large number of hydrogen bonds. A chiral dendritic diaethynic acid molecule with stimulus responsiveness is thus prepared and synthesized.

[0027] (2) This invention provides a method for preparing supramolecular chiral assemblies using chiral dendritic diaethynic acid molecules. Driven by the non-covalent interaction of chiral dendritic diaethynic acid molecules, supramolecular chiral assembly occurs, and the supramolecular chiral assembly can be regulated by temperature and light. This opens up a new way to create novel intelligent chiral nanomaterials with special structures and excellent properties.

[0028] (3) This invention provides a method for preparing covalent chiral polymers using supramolecular chiral assemblies, which endows amphiphilic dendritic macromolecules with the ability to undergo phototopological polymerization by using the bisacetylene unit provided by PCDA. Attached Figure Description

[0029] Figure 1 The PCDA-Lys-G1 prepared in Example 2 of this invention in DMSO-d6 1 HNMR spectrum, with the inset showing the structural formula of PCDA-Lys-G1;

[0030] Figure 2 The PCDA-Lys-G2 prepared in Example 3 of this invention in DMSO-d6 1 HNMR spectrum, with the inset showing the structural formula of PCDA-Lys-G2;

[0031] Figure 3 Example 4 of the present invention Figure 3 (a) and Example 5 Figure 3 (b) AFM image of the prepared supramolecular chiral assembly;

[0032] Figure 4 The CD spectra of the supramolecular chiral assemblies prepared in Examples 4 and 5 of this invention are shown.

[0033] Figure 5 This is a temperature-dependent CD spectrum of the supramolecular chiral assembly prepared in Example 4 of this invention, wherein... Figure 5 (a) for heating, Figure 5 (b) is for cooling;

[0034] Figure 6 This is a temperature-dependent CD spectrum of the supramolecular chiral assembly prepared in Example 5 of this invention, wherein... Figure 6(a) for heating, Figure 6 (b) is for cooling;

[0035] Figure 7 The images show the CD spectra of the supramolecular chiral assemblies prepared in Examples 4 and 5 of this invention under different illumination times. Figure 7 (a) indicates temperature increase. Figure 7 (b) is for cooling;

[0036] Figure 8 The image shows the temperature-dependent CD spectrum of the supramolecular chiral assembly prepared in Example 4 of this invention after 90 seconds of light irradiation. Figure 8 (a) indicates temperature increase. Figure 8 (b) is for cooling;

[0037] Figure 9 The image shows the temperature-dependent CD spectrum of the supramolecular chiral assembly prepared in Example 5 of this invention after 90 seconds of light irradiation. Figure 9 (a) indicates temperature increase. Figure 9 (b) To cool down. Detailed Implementation

[0038] 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.

[0039] To facilitate understanding, the abbreviations or names mentioned below will be explained first:

[0040] PCDA: 10,12-Ticosadecanyonic acid

[0041] DMAP: 4-Dimethylaminopyridine

[0042] DCM: Dichloromethane;

[0043] DiPEA: Diisopropylethylamine

[0044] HOBt: 1-Hydroxybenzotriazole

[0045] EDC·HCl: 1-Ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride

[0046] Example 1

[0047] This embodiment provides a method for synthesizing the compound Boc-Lys(PCDA)-OL for the preparation of chiral dendritic diacetylinic acid molecules.

[0048] First, the compound Boc-Lys(PCDA)-OMe was synthesized.

[0049] Second, synthesize the compound Boc-Lys(PCDA)-OH.

[0050] Third, the compound PCDA-Lys-G2-OL was synthesized.

[0051] The specific steps for synthesizing the compound Boc-Lys(PCDA)-OMe are as follows:

[0052] Two solutions were prepared and stirred separately at 0°C for 30 min. The two solutions were then mixed and stirred at 0.5°C for 20 min to obtain the OMe reaction solution. One solution was prepared by dissolving PCDA (0.75 g, 1.27 mmol) and DiPEA (0.33 g, 2.53 mmol) in dry DCM (10 mL). The other solution was prepared by dissolving Boc-Lys-OMe (0.35 g, 1.16 mmol) and HOBt (0.2 g, 1.5 mmol) in dry DCM (10 mL).

[0053] EDC·HCl (0.49 g, 2.53 mmol) was added to the OMe reaction solution, and the reaction was carried out under a nitrogen atmosphere until the reaction was determined to be complete by TLC plate. The reaction was then stopped, and the product was washed, dried and purified to obtain a colorless oily substance Boc-Lys(PCDA)-OMe.

[0054] The washing process involved washing with saturated NaHCO3 and KHSO4 solutions, followed by washing twice with saturated ammonium chloride solution; drying involved drying with anhydrous magnesium sulfate, filtering, and then evaporating the solvent; and purification involved using a silica gel column.

[0055] The above reaction principle is expressed as follows:

[0056]

[0057] The specific steps for synthesizing the compound Boc-Lys(PCDA)-OH are as follows:

[0058] The compound Boc-Lys(PCDA)-OMe (1.00 g, 1.62 mmol) was dissolved in a mixed solvent of methanol and deionized water (MeOH:H2O volume ratio of 5:1) (20 mL). LiOH·H2O (0.29 g, 6.8 mmol) was added at 0 °C and stirred under a nitrogen atmosphere until the reaction was complete as determined by TLC. The reaction was then stopped, and the solvent was removed, the pH was adjusted to acidity, extracted, and dried to obtain a colorless oily substance Boc-Lys(PCDA)-OH.

[0059] The solvent removal process involved evaporating methanol and water; pH adjustment involved using a saturated KHSO4 solution to adjust the pH of the product to 1-2; extraction involved extraction with dichloromethane; and drying involved drying with anhydrous magnesium sulfate, filtering, and then evaporating the solvent.

[0060] The steps for synthesizing compound PCDA-Lys-G2-OL are as follows:

[0061] Boc-Lys(PCDA)-OH (0.8 g, 1.46 mmol), DiPEA (0.33 g, 2.53 mmol), H-Lys-OL (0.15 g, 0.73 mmol), HOBt (0.20 g, 1.50 mmol), and EDC·HCl (0.49 g, 2.53 mmol) were mixed and stirred at 0 °C under a nitrogen atmosphere until the reaction was complete as determined by TLC. The reaction was then stopped, and the mixture was purified by silica gel column chromatography to obtain a colorless oily substance, PCDA-Lys-G2-OL.

[0062]

[0063] Example 2

[0064] This embodiment provides a method for preparing chiral dendritic diacetynyl acid molecules, specifically as follows:

[0065] Compounds PCDA-Lys-G2-OL (0.40 g, 0.34 mmol) and G1-COOH (0.20 g, 0.30 mmol) were dissolved in dry DCM (10 mL), followed by the addition of DMAP (0.02 g, 0.16 mmol) and EDC·HCl (0.23 g, 1.19 mmol). The reaction was carried out under nitrogen atmosphere and at 0 °C with continuous stirring. The reaction was stopped by TLC plate analysis to obtain crude product. After washing and purification, a colorless oily product (0.30 g, yield 53%) was obtained, namely chiral dendritic diaethynic acid molecule, labeled as PCDA-Lys-G1.

[0066] The washing process involved using a saturated sodium chloride solution, while the purification process involved using a silica gel chromatography column.

[0067] Test Analysis:

[0068] The 1H NMR spectrum of the product PCDA-Lys-G1 is shown below. Figure 1 As shown,

[0069] 1H NMR(500MHz,DMSO-d6)δ7.62(s,1H),7.45(s,2H),7.40-7.32(m,3H),4.18-4.14(m,21H),3.77-3.70(m,12H),3.46-3.42(m,32H), 3.32-3.23(m,6H),2.30(t,J=6.8Hz,7H),2.11-1.99(m,4H),1.57-1.32(m,38H),1.12(tt,J=7.0,4.3Hz,52H),0.95-0.80(m,6H).

[0070] The structural formula of the product PCDA-Lys-G1 is as follows:

[0071]

[0072] in,

[0073]

[0074] Example 3

[0075] This embodiment provides a method for preparing chiral dendritic diaethynic acid molecules. The synthesis steps are basically the same as in Example 2, except that:

[0076] G1-COOH is replaced with G2-COOH at a dosage of 0.71g and 0.30mmol.

[0077] The yield of the colorless oily product obtained was 0.25 g, with a yield of 47%, which was a chiral dendritic diaethynic acid molecule, labeled as PCDA-Lys-G2.

[0078] Test Analysis:

[0079] The 1H NMR spectrum of the product PCDA-Lys-G2 is shown below. Figure 2 As shown,

[0080] 1H NMR (500MHz, CDCl3) δ7.33 (dd, J=21.2, 4.4Hz, 7H), 6.33 (d, J=8.6Hz, 1H), 5.70 (s, 1H),5.16-4.95(m,4H),4.45(s,3H),4.13(ddd,J=15.3,5.8,4.5Hz,10H),4.05-3.7 8(m,11H),3.77-3.45(m,72H),3.32-3.14(m,5H),2.19(dt,J=45.8,7.4Hz,9H),1. 80(d,J=9.9Hz,9H),1.67-1.41(m,32H),1.40-1.15(m,60H),0.88(t,J=7.0Hz,6H).

[0081] The structural formula of the product PCDA-Lys-G2 is as follows:

[0082]

[0083] in,

[0084]

[0085] Example 4

[0086] This embodiment provides a method for preparing supramolecular chiral assemblies using the above-mentioned chiral dendritic diacetynyl acid molecules, specifically as follows:

[0087] The chiral dendritic diastynic acid molecules prepared in Example 2 above were mixed with acetone solution to prepare a solution with a concentration of 5 mg / mL. A certain amount of solution was pipetted onto a quartz plate and the acetone was allowed to evaporate completely to obtain a supramolecular chiral assembly (PCDA-Lys-G1Et).

[0088] Example 5

[0089] This embodiment provides a method for preparing supramolecular chiral assemblies using the above-mentioned chiral dendritic dicethynic acid molecules, specifically as follows:

[0090] The chiral dendritic diacetynyl acid molecules prepared in Example 3 above were mixed with acetone solution to prepare a solution with a concentration of 5 mg / mL. A certain amount of solution was pipetted onto a quartz plate and the acetone was allowed to evaporate completely to obtain a supramolecular chiral assembly (PCDA-Lys-G2Et).

[0091] Test Analysis:

[0092] I. Observation of supramolecular chiral assembly

[0093] like Figure 3The images shown are atomic force microscopy (AFM) images of the supramolecular chiral assemblies corresponding to Examples 4 and 5 above. It can be seen that PCDA-Lys-G1 assembled into fiber aggregates with an average diameter of 23 nm, while PCDA-Lys-G2 assembled into fiber aggregates with an average diameter of 20 nm. In comparison, the fiber aggregates formed by PCDA-Lys-G1 have a larger diameter.

[0094] II. Supramolecular chirality of assemblies

[0095] like Figure 4 As shown, the CD spectra of the supramolecular chiral assemblies corresponding to Examples 4 and 5 above were traced using a circular dichroism chromatograph. The assemblies of the two chiral dendritic diastynic acid molecules showed obvious chiral signals around 200 nm. Combined with the results of atomic force microscopy (AFM), it can be inferred that the two chiral dendritic diastynic acid molecules underwent supramolecular chiral assembly.

[0096] III. Temperature-responsiveness of the assembly

[0097] like Figure 5 and Figure 6 The figures shown are the temperature-dependent CD spectra of the supramolecular chiral assemblies corresponding to Examples 4 and 5, respectively. It can be seen that the CD signals of both supramolecular chiral assemblies decrease until they disappear as the temperature increases; during the cooling process, the CD signals reappear and gradually increase. Therefore, it can be concluded that the chirality of supramolecular chiral assemblies can be reversibly controlled by changing the temperature stimulus.

[0098] IV. Phototopological polymerization of assemblies

[0099] like Figure 7 The image shows the CD spectra of the supramolecular chiral assemblies corresponding to Examples 4 and 5 above at different irradiation times. These spectra were used to track the chiral changes of the two supramolecular chiral assemblies during the phototopological polymerization reaction. It can be seen that for the PCDA-Lys-G1 assembly, the CD signals at 500nm and 600nm gradually increased and then remained unchanged as the irradiation time increased, indicating that the diacetylene structure had reacted completely and the assembly was successfully converted into a covalent chiral polymer (dendritic PDA).

[0100] V. Temperature-responsiveness of covalent chiral polymers (dendritic PDAs)

[0101] like Figure 8 and Figure 9The figures shown are the temperature-dependent CD spectra of the supramolecular chiral assemblies corresponding to Examples 4 and 5 above after 90 s of illumination. It can be seen that for the supramolecular chiral assemblies irradiated with ultraviolet light for 90 s, the CD signals at 500 nm and 650 nm decrease during the temperature change; during the cooling process, the CD signals at 500 nm and 650 nm reversibly recover. Reversible control of the covalent chirality of dendritic PDAs can be achieved by changing the temperature stimulus.

[0102] In summary, this invention first provides a method for preparing stimulus-responsive chiral dendritic diacetylene acid molecules. Based on dendritic alkoxy ethers with specific topological structures, and taking advantage of the natural properties of the lysine moiety, a series of intelligent responsive chiral dendritic diacetylene acid molecules are prepared by introducing the diacetylene moiety.

[0103] The present invention also provides a method for achieving supramolecular chiral assembly of the above-mentioned chiral dendritic diaethynic acid molecules, which prepares supramolecular chiral assemblies through non-covalent interactions and realizes the regulation of supramolecular chiral assembly by external stimuli such as temperature and light.

[0104] Finally, the present invention also provides a method for preparing covalent chiral polymers from the above-mentioned supramolecular chiral assemblies, which transforms the supramolecular chiral assemblies into covalent chiral polymers with more stable structures through phototopological polymerization, thereby fixing the chirality and morphology of the assemblies.

[0105] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended embodiments and their equivalents.

Claims

1. A chiral dendritic diacetynyl acid molecule, characterized in that, The chiral dendritic diaethynic acid molecule comprises: a dendritic alkoxy ether moiety with a characteristic topological structure as a hydrophilic moiety, a lysine moiety with multiple hydrogen bond sites as a chiral source, and a photocrosslinkable diaethynic acid moiety as a hydrophobic moiety.

2. The chiral dendritic diacetynyl acid molecule according to claim 1, characterized in that, The structural formula of the chiral dendritic diacetylic acid molecule is: in, 3. The chiral dendritic diacetynyl acid molecule according to claim 1, characterized in that, The chiral dendritic diacetynyl acid molecule is stimuli-responsive.

4. A method for preparing chiral dendritic diacetynyl acid molecules, characterized in that the reactants... include: Compound PCDA-Lys-G2-OL and dendritic polyamide amine-carboxyl-linked block copolymer, The structural formula of compound PCDA-Lys-G2-OL is as follows:

5. The method for preparing chiral dendritic diacetynyl acid molecules according to claim 4, characterized in that, The dendritic polyamide amine-carboxyl block copolymer is G1-COOH or G2-COOH.

6. The method for preparing chiral dendritic diacetynyl acid molecules according to claim 4, characterized in that, The chiral dendritic diacetyl acid molecule is prepared by dissolving the reactants in DCM, adding DMAP and EDC·HCl, and reacting under a protective atmosphere at 0°C.

7. A method for preparing a supramolecular chiral assembly, characterized in that, The chiral dendritic diacetynyl acid molecule as described in any one of claims 1 to 3 is mixed with acetone to prepare an assembly solution. After the acetone evaporates, the supramolecular chiral assembly is obtained.

8. The method for preparing the supramolecular chiral assembly according to claim 7, characterized in that, The concentration of the assembly solution is 5 mg / mL.

9. The method for preparing a supramolecular chiral assembly according to any one of claims 7 to 8, characterized in that, The chirality of the supramolecular chiral assembly is reversibly tunable by temperature.

10. A method for preparing a covalent chiral polymer, characterized in that, The covalent chiral polymer is obtained by irradiating the supramolecular chiral assembly according to any one of claims 7 to 9 with light.

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