Manufacturing method and composition of carbon quantum dots that can enhance light energy

Abstract

This invention relates to a method for manufacturing carbon quantum dots that can enhance light energy, and the composition thereof. The method includes the following steps: mixing a carbon-based compound with an embedded atom compound; heating for a pretreatment reaction; adding deionized water and stirring thoroughly before allowing to stand; filtering to remove the solid; mixing the solid with a surface-modifying solvent; adding a polymer; and then placing the mixture in an autoclave at a specific temperature for reaction. Subsequent drying and curing yields solid carbon quantum dots. This method aims to enhance the quantum efficiency of carbon quantum dots by adding a polymer, thereby increasing their light energy. The composition includes the raw carbon-based compound and the embedded atom compound, a surface-modifying solvent, and a polymer. This invention offers advantages such as making carbon quantum dots controllable, slowing down deactivation, and enhancing light energy.

Description

[Technical Field]

[0001] The present invention provides a method for manufacturing carbon quantum dots that can enhance light energy and its composition, particularly by adding polymers during the manufacturing process of carbon quantum dots to improve the dispersibility of carbon quantum dots, slow down the process of carbon quantum dots losing activity, and improve the quantum efficiency of carbon quantum dots to enhance light energy. [Previous Technology]

[0002] Photodynamic therapy is a method of treating diseases by selectively using photosensitizers in combination with light of a specific wavelength. Photosensitizers are photoactive compounds that release active substances, such as free radicals and cations, after absorbing light of a specific wavelength. These active substances have redox or oxygen transfer reactivity and produce phototoxicity on specific biomolecules (such as bacteria, fungi, macula, cancer cells, etc.), destroying their harmful substances and thus achieving a therapeutic effect.

[0003] The selection of photosensitizers is a crucial consideration in photodynamic therapy. Traditional photosensitizers may have toxicity or side effects, and organic photosensitizers are easily damaged by light, resulting in poor photostability. Furthermore, some photosensitizers are sensitive to specific wavelengths of light, limiting their applicability to various wavelengths. Moreover, the optical properties of organic photosensitizers are difficult to adjust chemically. Therefore, improving the precision and efficacy of photodynamic therapy requires developing innovative photosensitizing materials or optimizing optical design, methods that are time-consuming or have limited effectiveness. Carbon quantum dots, by controlling the type of surface-modifying solvent, can produce carbon quantum dots with different wavelengths of fluorescence, enabling their application in various fields and uses.

[0004] Furthermore, given the good biocompatibility, photostability and high tunability of carbon quantum dots, how to regulate and improve the quantum properties of carbon quantum dots is of great importance to those engaged in this industry, and needs to be redesigned and studied for effective application. [Summary of the Invention]

[0005] Therefore, in view of the above-mentioned deficiencies, the inventor collected relevant information, conducted multiple evaluations and considerations, and based on years of experience accumulated in this industry, through continuous trial and modification, added polymers to the carbon quantum dot manufacturing process to improve quantum efficiency and dispersibility, and designed this manufacturing method and its components that can enhance light energy carbon quantum dots.

[0006] The primary objective of this invention is to provide a method for manufacturing carbon quantum dots that enhance light energy, comprising the following steps: mixing a carbon-based compound and an embedded atom compound in a certain proportion; heating to a first preset temperature for a pretreatment reaction lasting for a first preset time; adding a first preset proportion of deionized water to increase volume, stirring thoroughly, and allowing to stand for a second preset time; filtering to remove the solid; mixing the solid with a surface-modifying solvent in a certain proportion; mixing the solution with a polymer in a certain proportion; placing it in an autoclave for a third preset time and reacting at a second preset temperature; and drying and solidifying the liquid to obtain a solid product. The carbon quantum dots manufactured by the aforementioned steps can enhance light energy by adding polymers of different molecular weights to improve the quantum efficiency and dispersibility of the carbon quantum dots to varying degrees.

[0007] A secondary objective of the present invention is that, if the desired product is a liquid, the step of "drying and solidifying the liquid to obtain a solid product" is changed to "cooling the liquid and then removing it, and then filtering it to obtain the liquid product".

[0008] Another object of the present invention is that the ratio of carbon-based compound to embedded atom compound is "2-15 parts carbon-based compound" to "2-30 parts embedded atom compound", and the ratio of solids, surface-modifying solvent and polymer is "5-15 parts solids" to "10-30 parts surface-modifying solvent" to "2-10 parts polymer".

[0009] Another object of the present invention is that the first preset temperature is 70-150 degrees, the second preset temperature is 180 degrees, the first preset time is 16-24 hours, the second preset time is 24-72 hours, the third preset time is 8-15 hours, and the first preset ratio is that the volume of the solution after adding deionized water becomes 6-15 times the volume of the solution in the previous step.

[0010] Another major objective of the present invention is to provide a component for enhancing the light energy of carbon quantum dots, comprising a raw material carbon-based compound and an embedded atom compound, as well as a surface-modifying solvent and a polymer.

[0011] Another secondary objective of the present invention is that the surface-modifying solvent is a hydrophilic solvent such as sodium hydroxide solution, deionized water, ethanol, or a hydrophobic solvent such as DMF (dimethylformamide) or DMAC (dimethylacetamide), and the polymer is PEG (polyethylene glycol), PEO (polyethylene oxide), PVDF (polyvinylidene fluoride), CA (cellulose acetate), PMMA (polymethyl methacrylate), PEA (polyethylene adipate), PBA (polybutylene adipate), IPDI (isocyanate), or acrylate.

Implementation Method

[0013] In order to achieve the above-mentioned objectives and effects, the technical means and methods adopted by the present invention are described in detail below with reference to the preferred embodiments of the present invention, so as to facilitate a complete understanding.

[0014] Please refer to Figure 1, which is a flowchart of the manufacturing method of the carbon quantum dots that can enhance light energy according to the present invention. As can be clearly seen from the figure, the present invention includes the following steps:

[0015] Step 11: Mix a carbon-based compound with an embedded atom compound in a certain proportion.

[0016] In this embodiment, the proportions of the parts are all weight proportions (g / g). It should be noted that the carbon-based compounds are selected from pyrene, benzene, triphenylene, citric acid, glucose, cellulose, p-ethylenediamine, o-ethylenediamine, m-ethylenediamine, and triethylamine; the embedded atom compounds contain elements with atomic weights greater than carbon, such as nitrogen, boron, or sulfur. In this embodiment, compounds such as urea, uric acid, nitrogen, ammonia, nitric acid, phosphoric acid, boric acid, or sulfuric acid are used. The ratio of the carbon-based compounds to the embedded atom compounds is "2-15 parts carbon-based compounds" to "2-30 parts embedded atom compounds", wherein the preferred ratio is "5-10 parts carbon-based compounds" to "5-20 parts embedded atom compounds".

[0017] Step 12: Heat to a first preset temperature and perform a pretreatment reaction for a first preset time.

[0018] In this embodiment, the first preset temperature is 70-150 degrees Celsius, preferably 80-120 degrees Celsius. The first preset time is 16-24 hours, preferably 17-20 hours, which is the temperature environment and duration of the pretreatment reaction before heating.

[0019] Step 13: Add a first preset ratio of deionized water to increase the volume, stir thoroughly and let stand for a second preset time.

[0020] In this embodiment, the first preset ratio is "1 unit of the original volume of this step" to "6-15 times the volume after adding deionized water", that is, the volume after adding deionized water is 6-15 times that before adding it. The preferred ratio is "1 unit of the original volume of this step" to "8-10 times the volume after adding deionized water". The second preset time is 24-72 hours, preferably 36-60 hours, which is the duration of standing.

[0021] Step 14: Filter and remove solids.

[0022] The above-mentioned filtration process is for separating solids. In this embodiment, a PVDF (polyvinylidene fluoride) membrane with a pore size of 0.22 micrometers is used for filtration. The pore size of 0.22 micrometers is selected for this embodiment. In other cases, it is not limited to this. Any method that can separate solids is applicable.

[0023] Step 15: Mix the solid with a surface-modifying solvent in a certain proportion.

[0024] In this embodiment, the ratio is "5-15 parts solids" to "10-30 parts surface-modifying solvent", preferably "7-12 parts solids" to "10-30 parts surface-modifying solvent". The surface-modifying solvent is DMF (dimethylformamide).

[0025] Step 16: Mix the solution with a polymer in a certain proportion.

[0026] In this embodiment, the above-mentioned ratio is based on the ratio of the solid product and the surface-modifying solvent in step 15, with the addition of "2-10 parts of polymer", preferably "4-8 parts of polymer". The polymer is PEG (Polyethylene glycol), PEO (Polyethylene oxide), PVDF (Polyvinylidene fluoride), CA (Cellulose acetate), PMMA (Polymethyl methacrylate), PEA (Polyethylene adipate), PBA (Polybutylene adipate), IPDI (Isophorone diisocyanate), or acrylate.

[0027] Step 17: Place it in a high-pressure reactor and react it for a third preset time and in a second preset temperature environment.

[0028] In this embodiment, the third preset time is 8-15 hours, preferably 10-13 hours, and the second preset temperature is 180 degrees. This is the time and temperature for placing the autoclave.

[0029] Step 18: Dry and solidify the liquid to obtain a solid product.

[0030] In this embodiment, the drying temperature is 60-150 degrees Celsius. Any method that can dry liquid to obtain solid product is feasible and is not limited to this temperature range.

[0031] If a liquid product is to be generated, step 18 "drying and solidifying the liquid to obtain a solid product" is changed to "cooling the liquid and taking it out, and then filtering it to extract the liquid product". In this embodiment, the filtration method is to filter the liquid product with a membrane with a pore size of 50 nanometers to 220 nanometers.

[0032] The above-mentioned thin film is used for separating the required liquid. Its pore size of 50 nanometers to 220 nanometers is also selected for this embodiment. It is not limited to this in other cases. Any method that can separate the required liquid is applicable.

[0033] The following is an embodiment of the present invention. The polymer added in step 16 is divided into four groups: CQD-P without polymer, CQD-1 with polymer added and a molecular weight of 3,000 to 8,000, CQD-2 with polymer added and a molecular weight of 8,000 to 20,000, and CQD-3 with polymer added and a molecular weight of 200,000 to 400,000.

[0034] Please refer to Figure 2, the X-ray diffraction analysis diagram of the present invention. The crystal structure is analyzed by X-ray diffraction pattern. If the area of ​​the peak in the pattern is larger, the content of the crystal phase is greater. Therefore, the following conclusion can be drawn from Figure 2: As the molecular weight increases, the proportion of carbon 002 crystal plane decreases while carbon 101 and carbon 004 increase slightly. However, the CO crystal form (131) provided by the polymer also gradually increases. The situation is the same for molecular weights of 8,000 to 20,000 (CQD-2) and 200,000 to 400,000 (CQD-3). Therefore, the quantum efficiency of molecular weights of 8,000 to 20,000 and 200,000 to 400,000 is slightly the same.

[0035] Raman spectroscopy is used to study the vibrations and rotations of material molecules or crystal lattices. The D and G peaks are characteristic peaks in Raman spectroscopy. The D peak is positively correlated with structural defects in carbon materials, while the G peak reveals the lattice and layered structure of carbon materials. The D / G ratio refers to the intensity ratio of the D and G peaks. Generally, a higher D / G ratio indicates more material defects and lower crystallinity. The G / D ratio, on the other hand, is the intensity ratio of the G and D peaks and is related to crystallinity and lattice integrity. Please refer to Figure 3, the Raman spectrum of this invention, and the table below. It is evident that when the molecular weight of the polymer added during the process increases, the 2D multilayer irregular crystal planes increase. Unmodified CQD (CQD-P) has no 2D crystal form. Therefore, increasing the proportion of 2D multilayer irregularities in the material can significantly improve quantum efficiency. D / G G / D CQD-P 0.98 1.03 CQD-1 0.67 1.5 CQD-2 0.67 1.48 CQD-3 0.68 1.47

[0036] Please refer to Figure 4, the fluorescence spectrum of the present invention. The fluorescence spectrum represents the excitation of molecules by light sources of different wavelengths, thereby emitting fluorescence. As can be clearly seen from the figure, when the molecular weight of the added polymer increases, its fluorescence intensity will increase under the same illumination. Since polymers can act as energy transfer agents, effectively transferring energy, under fluorescence, the polymer absorbs light energy and transfers it to the carbon quantum dots, thus enhancing the photoexcitation efficiency of the carbon quantum dots. This results in more photons being absorbed and converted into fluorescence, thereby increasing its fluorescence intensity.

[0037] Please refer to Figure 5(A) for transmission electron microscopy images of polymers with molecular weights of 3000 to 8000 (CQD-1) according to the present invention, and Figure 5(B) for transmission electron microscopy images of polymers with molecular weights of 8000 to 20,000 (CQD-2) according to the present invention. The carbon quantum dots resulting from polymers with molecular weights of 8000 to 20,000 (CQD-2) exhibit better dispersion (smaller fixed particle size of individual carbon quantum dots). The better the dispersion of carbon quantum dots, the higher the quantum efficiency. Therefore, it can be concluded that the higher the molecular weight of the polymer, the better the quantum efficiency. At the same time, the polymer can protect the carbon quantum dots and slow down the rate at which the carbon quantum dots lose their activity.

[0038] As shown in Figure 2, the quantum efficiencies of molecular weights from 8,000 to 20,000 and from 200,000 to 400,000 are roughly the same. Figure 3 demonstrates that increasing the proportion of irregular 2D multilayer structures in the material can significantly improve the quantum efficiency. Figure 4 shows that polymers can effectively transfer energy to carbon quantum dots as energy transfer agents. Figures 5(A) and 5(B) show that the higher the molecular weight of the polymer, the better the dispersibility and the better the quantum efficiency. Therefore, this embodiment includes raw material carbon-based compounds, embedded atom compounds, surface-modifying solvents, and polymers that enhance the light energy of carbon quantum dots. With the addition of polymers with a molecular weight of 8,000 or higher, it is evident that the increase in molecular weight leads to an increase in the quantum efficiency and dispersibility of the carbon quantum dots, thereby enhancing their light energy. The surface-modifying solvent is a hydrophilic solvent such as sodium hydroxide solution, deionized water, or ethanol, or a hydrophobic solvent such as DMF (dimethylformamide) or DMAC (dimethylacetamide), and the polymer is PEG, PEO, PVDF, CA, PMMA, PEA, PBA, IPDI, or acrylate.

[0039] The above detailed description is only for the purpose of describing a preferred embodiment of the present invention. However, this embodiment is not intended to limit the scope of the patent application of the present invention. All other equivalent changes and modifications made without departing from the spirit of the technology disclosed in the present invention should be included in the patent scope covered by the present invention.

[0040] In summary, the above-mentioned method for manufacturing carbon quantum dots that can enhance light energy and its components can indeed achieve their effects and purposes. Therefore, this invention is indeed a highly practical invention. In order to meet the application requirements for an invention patent, this application is filed in accordance with the law. We hope that the Examination Board will grant this application as soon as possible to protect the inventor's hard work. If the Examination Board has any questions, please do not hesitate to write to us for guidance. The inventor will do his best to cooperate. We appreciate your help. [Simplified Explanation of the Diagram]

[0012] [Figure 1] is a flowchart of the present invention. [Figure 2] is an X-ray diffraction analysis diagram of the present invention. [Figure 3] is a Raman spectrum of the present invention. [Figure 4] is a fluorescence spectrum of the present invention. [Figure 5(A)] is a transmission electron microscope image of a polymer with a molecular weight of 6000 according to the present invention. [Figure 5(B)] is a transmission electron microscope image of a polymer with a molecular weight of 10,000 according to the present invention.

Claims

1. A method for manufacturing carbon quantum dots that enhance light energy, comprising the following steps: (A) mixing a carbon-based compound with an embedded atom compound in a certain proportion, wherein the carbon-based compound is selected from pyrene, benzene, triphenylene, citric acid, glucose, cellulose, or triethylamine, and the embedded atom compound is urea, uric acid, nitrogen, ammonia, nitric acid, phosphoric acid, boric acid, or sulfuric acid; (B) heating to a first preset temperature for a pretreatment reaction lasting for a first preset time; (C) adding a first preset proportion of deionized water to increase the volume, stirring thoroughly, and then allowing it to stand for a second preset time, wherein the second preset proportion is 6-15 times the volume of the solution without added deionized water, and the second preset time is 24-72 hours; (D) filtering to remove the solid; (E) mixing the solid with a surface-modifying solvent in a certain proportion; (F) mixing the solution with a polymer in a certain proportion, wherein the polymer is PEG (Polyethylene glycol) or PEO (Polyethylene oxide). (G) The mixture is placed in an autoclave and reacted for a third preset time at a second preset temperature; (H) The liquid is dried and solidified to obtain a solid product.

2. The method for manufacturing carbon quantum dots that can enhance light energy as described in claim 1, wherein the first preset temperature in step (B) is 70-150 degrees and the first preset time is 16-24 hours.

3. The method for manufacturing carbon quantum dots that can enhance light energy as described in claim 1, wherein the surface modification solvent in step (E) is a hydrophilic solvent, and the hydrophilic solvent is sodium hydroxide solution, deionized water, ethanol, or a hydrophobic solvent, and the hydrophobic solvent is DMF (dimethylformamide) or DMAC (dimethylacetamide).

4. The method for manufacturing carbon quantum dots that can enhance light energy as described in claim 1, wherein the third preset time in step (G) is 8-15 hours and the second preset temperature is 180 degrees.

5. The method for manufacturing carbon quantum dots that can enhance light energy as described in claim 1, wherein step (H) is changed to: cooling the liquid and then removing it, and then filtering the liquid product.

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