Chiral manganese-based nanomaterial based on ribose ligand and synthesis method thereof
By self-assembling riboligands with potassium permanganate and CTAB under alkaline conditions to form chiral tunable nanomaterials, the problems of complex preparation and difficult signal modulation of chiral nanomaterials have been solved, realizing simple preparation and efficient detection of chiral nanomaterials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2024-11-27
- Publication Date
- 2026-05-29
AI Technical Summary
The preparation of existing chiral nanomaterials is complex and the chiral signal is difficult to control, and there is a lack of research on the interaction between chiral substances.
Using ribose as a chiral ligand, it self-assembles with potassium permanganate and CTAB under alkaline conditions to form chiral manganese-based nanoparticles, and then prepares chiral nanomaterials through redox reactions.
We have achieved the preparation of simple chiral nanomaterials with good chiral optical properties and high asymmetry factor, which can be used for the detection of glutathione.
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Figure CN122102213A_ABST
Abstract
Description
Technical Field
[0001] This application relates to a chiral manganese-based nanomaterial based on riboglycolic ligands and its synthesis method, belonging to the field of nanomaterial synthesis and self-assembly science and technology. Background Technology
[0002] Chirality is one of the essential properties of nature. Almost all proteins in living organisms are composed of left-handed amino acids, while carbohydrates are mostly right-handed. The famous double helix structure of DNA is always a right-handed helix. Chirality plays a very important role in fields such as biochemistry, organic chemistry, catalysis, and pharmacy.
[0003] Chiral nanomaterials are a new class of nanomaterials. With the development of nanotechnology, chirality has been transferred from molecular-scale components to the nanoscale, and these chiral structures endow these materials with unique surface chemistry, thermal, and chiral optical properties. Therefore, in recent years, the preparation of chiral nanomaterials and their applications in biomedicine, sensing and analysis, asymmetric catalysis, and other fields have received widespread attention. Currently, the preparation of chiral materials is relatively mature, but little is known about the generation of chirality, the regulation of chiral signals, and the interactions between chiral substances. Summary of the Invention
[0004] To address the challenges of controlling chiral signals and complex fabrication in existing chiral nanomaterial technologies, this application proposes a chiral tunable manganese-based chiral nanoparticle technology. This technology utilizes ribose as a chiral ligand, undergoing redox reactions and self-assembly under alkaline conditions to achieve simple preparation of chiral tunable nanomaterials. These nanomaterials possess excellent chiral optical properties, a high asymmetry factor, and exhibit a linear response to glutathione, making them suitable for glutathione detection.
[0005] The technical solution adopted in this application is as follows:
[0006] According to a first aspect of this application, a chiral manganese-based nanomaterial based on riboligands is provided, wherein the chiral manganese-based nanomaterial is formed by the self-assembly of raw materials containing chiral ligands, CTAB, and potassium permanganate under alkaline conditions to form chiral nanoparticles with tunable chirality.
[0007] Optionally, the particle size of the chiral manganese-based nanomaterial based on riboglycolic ligands is 100–300 nm.
[0008] Optionally, the characteristic peak of the circular dichroism spectral signal of the chiral manganese-based nanomaterial based on ribose ligands is 450–500 nm.
[0009] Optionally, the riboligand has a D configuration and / or an L configuration.
[0010] Optionally, the content of the riboligand is 1–3 mmol / L.
[0011] According to another aspect of this application, a method for preparing the above-mentioned chiral manganese-based nanomaterials based on riboglycolic ligands is provided, comprising the following steps:
[0012] A potassium permanganate aqueous solution was added to an aqueous solution containing ribose and CTAB to obtain a raw material solution, which was then reacted to obtain the chiral manganese-based nanomaterial containing the ribose ligand.
[0013] Optionally, the feed liquid contains, in molar parts:
[0014] Ribose 0.5–2 moles;
[0015] CTAB 0.2–0.4 moles;
[0016] Potassium permanganate 0.2-0.3 moles.
[0017] Optionally, the stirring conditions include: reacting at 35–40°C for 4–6 hours under stirring conditions.
[0018] Optionally, the step further includes purification:
[0019] (1) After the reaction is complete, the product is centrifuged at 9000-12000 rpm for 5-20 min;
[0020] (2) Repeat step (1) at least once to resuspend the precipitate obtained after centrifugation in water.
[0021] Optionally, the steps are as follows:
[0022] Mix 0.5–2.0 ml of an aqueous solution containing 0.1 mol / L ribose and 0.2–0.4 ml of an aqueous solution containing 0.1 mol / L LCTAB, then add 2–3 ml of an aqueous solution containing 0.01 mol / L potassium permanganate to obtain a raw material solution. React to obtain the chiral manganese-based nanomaterials of the ribose ligand.
[0023] The beneficial effects of this application include:
[0024] This application provides chiral manganese-based nanomaterials based on ribose ligands and their synthesis method. The preparation is simple, and the materials exhibit good chiral optical properties with tunable chirality. By changing the configuration and amount of ribose raw material, the chiral structure and circular dichroism signal of the resulting chiral nanoparticles can be adjusted. This application uses ribose as a ligand and assembles materials with tunable chiral nanostructures through a redox reaction of potassium permanganate and CTAB under alkaline conditions. This is of great significance for the development of more chiral materials. Attached Figure Description
[0025] Figure 1 The circular dichroism spectrum of the chiral manganese-based nanomaterials of this application;
[0026] Figure 2 The ultraviolet-visible absorption spectrum of the chiral manganese-based nanomaterials of this application;
[0027] Figure 3 Image of the asymmetry factor of the chiral manganese-based nanomaterials of this application;
[0028] Figure 4 The image shows a scanning electron microscope (SEM) image of the chiral manganese-based nanomaterials of this application.
[0029] Figure 5 The infrared spectrum of the chiral manganese-based nanomaterials of this application;
[0030] Figure 6 The image shows the X-ray diffraction (XRD) spectrum of the chiral manganese-based nanomaterials of this application.
[0031] Figure 7 Images showing the asymmetry factor of chiral manganese-based nanomaterials prepared with different amounts of sugar raw materials according to this application. Detailed Implementation
[0032] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0033] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.
[0034] Unless otherwise specified, all test methods are standard and all instrument settings are those recommended by the manufacturer.
[0035] Example 1: Synthesis and Purification of Chiral Manganese-Based Nanomaterials Based on Riboligands
[0036] Under 40℃ water bath conditions, water, 0.1 mol / L CTAB aqueous solution (1.5 mL), and 0.1 mol / L ribose aqueous solution (0.2 mL, ribose composed of equimolar amounts of L-ribose and D-ribose) were added sequentially to the flask. The mixture was stirred for 10 min, and then 0.01 mol / L potassium permanganate solution (3 mL) was added. After stirring and reacting for 4 hours, the mixture was centrifuged at 10000 rpm for 10 min. This process was repeated twice. The resulting precipitate was resuspended and stored in ultrapure water, which is the chiral manganese-based nanomaterial based on ribose ligands.
[0037] Test Example 1: Characterization of the physical properties of chiral manganese-based nanomaterials with sugar ligands
[0038] Circular dichroism spectroscopy characterization: The purified chiral manganese-based nanomaterial dispersion based on riboglycolic ligands was diluted to 10 μg / mL. Using ultrapure water as a baseline, the scanning range was 200 to 800 nm, the scanning step size was 1 nm, and the scanning speed was 0.5 s / nm. The results are as follows: Figure 1 As shown, the chiral manganese-based nanomaterial based on riboglycolic ligands has a distinct circular dichroism signal that is different from that of riboglycolic chiral ligands, with its main peak between 450-500 nm.
[0039] UV-Vis absorption spectroscopy characterization: The purified chiral manganese-based nanomaterial dispersion based on ribose ligands was diluted to 10 μg / mL. Using ultrapure water as a baseline, the scanning range was 200 to 800 nm, the scanning step size was 1 nm, and the scanning speed was 1 sec / nm. The results are as follows: Figure 2 As shown, the material absorbs light in the visible region, with the main peak around 400-500 nm.
[0040] The asymmetry factor image was calculated using the circular dichroism spectrum and UV-Vis absorption spectrum described above. The calculation formula is: CD / (32980*UV). The result is as follows: Figure 3 As shown, the asymmetry factor can reach 0.003.
[0041] Scanning electron microscopy characterization: The purified chiral manganese-based nanomaterial dispersion based on riboglycolic ligands was diluted to 300 μg / mL, and 7 μL was dropped onto the surface of a silicon wafer. After drying, the wafer was imaged under an accelerating voltage of 5 kV. The results are as follows: Figure 4 As shown (scale 100nm), the nanomaterial is spherical with a particle size of 100-300nm.
[0042] Infrared spectroscopy characterization: The purified chiral manganese-based nanomaterial dispersion based on ribose ligands was centrifuged, the precipitate was vacuum dried for 12 h, and then ground into a powder sample. The ATR method was used to analyze the spectroscopy results at 400 to 4000 cm⁻¹. -1 Scan within the range, results as follows Figure 5 As shown, the material is at 3340cm. -1 The broad peak is due to the -COOH stretching vibration, at 1640 cm⁻¹. -1 The peak may be due to the -C=O stretching vibration, because the coordination with metal ions shifts to higher wavenumbers.
[0043] XRD characterization: The purified chiral manganese-based nanomaterial dispersion based on ribose ligands was centrifuged, the precipitate was vacuum dried for 12 h, and then ground into a powder sample. XRD was performed within the range of 5 to 90 degrees. The results are as follows: Figure 6 As shown, the material's spectrum closely resembles the standard spectrum of MnO2.
[0044] Examples 2-5
[0045] The preparation method was the same as in Example 1, with the amounts of ribose aqueous solution used being 0.1 mL, 0.2 mL, 0.25 mL, 0.3 mL, and 0.4 mL respectively. A new series of chiral manganese-based nanomaterials based on ribose ligands were prepared, and then tested under the same conditions as in Example 1. The results are as follows. Figure 7 As shown, the asymmetry factor of the material changes with the amount of ribose added, the characteristic peak of the circular dichroism signal shifts with the amount of ribose added, and chiral signal inversion occurs within a certain range. Therefore, this application demonstrates that by changing the amount of ribose added, the chiral structure and circular dichroism signal of the obtained chiral nanoparticles can be adjusted.
[0046] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A chiral manganese-based nanomaterial based on riboglycolic ligands, characterized in that, The chiral manganese-based nanomaterials based on riboligands are formed by the self-assembly of raw materials containing chiral ligands, CTAB, and potassium permanganate under alkaline conditions to form chiral nanoparticles with tunable chirality.
2. The chiral manganese-based nanomaterial based on riboglycolic ligands according to claim 1, characterized in that, The chiral manganese-based nanomaterials based on riboglycolic ligands have a particle size of 100–300 nm.
3. The chiral manganese-based nanomaterial based on riboglycolic ligands according to claim 1, characterized in that, The characteristic peak of the circular dichroism spectrum of the chiral manganese-based nanomaterial based on riboglycolic ligands is 450–500 nm.
4. The chiral manganese-based nanomaterial based on riboglycolic ligands according to claim 1, characterized in that, The riboligand has a D configuration and / or an L configuration.
5. The chiral manganese-based nanomaterial based on riboglycolic ligands according to claim 1, characterized in that, The content of the riboligand is 1–3 mmol / L.
6. The method for preparing chiral manganese-based nanomaterials based on riboglycolic ligands according to any one of claims 1 to 5, characterized in that, Includes the following steps: A potassium permanganate aqueous solution was added to an aqueous solution containing ribose and CTAB to obtain a raw material solution, which was then reacted to obtain the chiral manganese-based nanomaterial containing the ribose ligand.
7. The preparation method according to claim 6, characterized in that, The feed liquid contains, in molar amounts: Ribose 0.5–2 moles; CTAB 0.2–0.4 moles; Potassium permanganate 0.2-0.3 moles.
8. The preparation method according to claim 6, characterized in that, The stirring conditions include: reacting at 35–40°C for 4–6 hours under stirring conditions.
9. The preparation method according to claim 6, characterized in that, The steps also include purification: (1) After the reaction is complete, the product is centrifuged at 9000-12000 rpm for 5-20 min; (2) Repeat step (1) at least once to resuspend the precipitate obtained after centrifugation in water.
10. The preparation method according to claim 6, characterized in that, The steps are as follows: Mix 0.5–2.0 ml of an aqueous solution containing 0.1 mol / L ribose and 0.2–0.4 ml of an aqueous solution containing 0.1 mol / L LCTAB, then add 2–3 ml of an aqueous solution containing 0.01 mol / L potassium permanganate to obtain a raw material solution. React to obtain the chiral manganese-based nanomaterials of the ribose ligand.