• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    The invention discloses a method of making the carbon dots with bromopropene and imidazole compounds and a product thereof. In particular, the carbon dots are produced by reaction immediately after mixing bromopropene and imidazole compounds. The synthesis process of the method of the present invention is simple and green, and the synthesized carbon points have good fluorescence performance and light stability. A new method for the synthesis of carbon points is provided.
    公开号:BE1027470B1
    申请号:E20205537
    申请日:2020-07-17
    公开日:2021-04-19
    发明作者:Jiucun Chen；Zhiqin Deng；Yanzi Jin
    申请人:Univ Southwest；
    IPC主号:
    专利说明:

    Process for making carbon dots with bromopropene and imidazole compounds and its product
    TECHNICAL FIELD The invention relates to the production of nanoluminescent materials, in particular to a method for producing carbon dots with bromopropene and imidazole compounds, as well as the products produced by the method.
    BACKGROUND ART Fluorescent nanomaterials have attracted the attention of science because of their wide range of applications. Compared with conventional semiconductor quantum dots and aromatic fluorescent dyes, carbon dots have better properties such as low or no toxicity, high chemical inertness and good biological compatibility, strong photobleaching resistance, excellent photoelectric performance and easy surface modification and the like, and they show great potential in the fields of biological Imaging, chemistry / biosensors, drug / gene delivery, optoelectronic devices and the like. Considerable progress has been made in the development of synthetic methods and two manufacturing ideas have been combined. The "top-down" process breaks down complex structures into carbon dots, including laser etching, thermal decomposition, electrolytic stripping and
    Arc discharge. The "bottom-up" process synthesizes low molecular weight raw materials by polymerization-agglomeration-dehydration-carbonization processes, including hydrothermal / solvent-thermal processes, microwave synthesis, dehydration and carbonization with strong acid, etc. Both methods are possible through external energy transfer, so it is always worthwhile yet to find a simple, quick, environmentally friendly, and user-friendly synthesis method.
    SUMMARY OF THE PRESENT INVENTION In view of the above, it is an object of the present invention to provide a method for producing carbon dots with bromopropene and imidazole compounds, the second object of the present invention being to provide carbon dots produced by the above method.
    In order to achieve the above objects, the present invention provides the following technical solutions:
    1. A method for producing carbon dots with bromopropene and imidazole compounds, wherein the bromopropene and imidazole compounds react immediately after mixing to produce carbon dots.
    Preferably the imidazole compound is at least one of 1-vinylimidazole or 1-methylimidazole.
    The bromopropene and imidazole compounds are preferably mixed in a volume ratio of 1: 1 to 1: 3. The reaction temperature is preferably 5 to 40 ° C.
    Preferably, the mixing can use any existing mixing method, and more preferably the mixing is carried out by stirring.
    The reaction time is preferably at least 1 s, more preferably the reaction time is 1 s to 10 min.Preferably, carbon points are further collected after the reaction, in particular cooling the reaction solution, centrifuging, filtering, dialyzing and freeze-drying to obtain carbon point powder. Preferably centrifugation at 8000 rpm for 10 to 20 minutes, filtration with 0.22 µm microporous filter membrane and dialysis with a dialysis bag with a molecular weight limit of 500 Da for 24 to 48 hours.
    2. The carbon point generated by the process.
    Preferably the average particle size is 116 nm and the particle size distribution range is 8 to 14 nm.
    The advantageous effect of the present invention is that the present invention discloses a method for producing carbon dots with bromopropene and imidazole compounds. The method of the invention can add carbon points directly by stirring
    Maintain room temperature, the synthesis steps are simple, the conditions are controllable and in which no energy consumption is required, this is environmentally friendly and has a short reaction time, in which carbon points are generated within seconds, whereby a new synthesis method for carbon point synthesis has been found. The carbon points obtained represent advantages such as good fluorescence performance and water solubility.
    BRIEF DESCRIPTION OF THE DRAWING In order to make the objects, technical solutions and advantageous effects of the present invention more clear, the present invention provides the following drawings for illustrative purposes: Fig. 1 is a transmission electron microscope picture of carbon dots produced by the present invention.
    Figure 2 is a histogram of the particle size distribution of carbon dots produced by the present invention. Fig. 3 is a UV absorption spectrum of carbon dots produced by the present invention. Fig. 4 is an infrared absorption spectrum of carbon dots produced by the present invention.
    Figure 5 shows an emission spectrum of the carbon dots produced by the present invention at various excitation wavelengths.
    Fig. 6 is a graph showing the quantum yield data processing of quinine sulfate standard samples. Figure 7 is a diagram of the quantum yield data processing of the carbon dots produced by the present invention.
    FIG. 8 is an ultraviolet absorption spectrum of carbon dots prepared in Example 4. FIG.
    9 shows an emission spectrum of the carbon dots produced in Example 4 at various excitation wavelengths.
    DETAILED DESCRIPTION The present invention is explained in more detail below with reference to the drawings and specific embodiments so that those skilled in the art can better understand and implement the present invention, but the cited embodiments are not intended to limit the present invention.
    Example 1 The method of making carbon dots with bromopropene and 1-vinylimidazole comprising the following steps:
    (1) measuring 5 ml of bromopropene and 5 ml of 1-vinylimidazole separately, pouring into a 50 ml beaker, stirring rapidly to mix the solution evenly, standing still for the reaction to obtain the reaction solution containing carbon dots; (2) After naturally cooling the reaction solution obtained in step (1), centrifuging for 10 minutes at 8000 rpm in a high-speed centrifuge to obtain a supernatant, then filtering the supernatant with a 0.22 µm microporous filter membrane; The filtrate is dialyzed by means of a dialysis bag with a molecular weight limit of 500 Da for 48 hours and then freeze-dried to obtain the carbon point powder, and finally a part of the carbon point powder is dispersed each with ultrapure water and ethanol to obtain a carbon point dispersion liquid, store at 4 ° C.
    Example 2 The method for making carbon dots with bromopropene and 1-vinylimidazole comprising the following steps:
    (1) measure 5 ml of bromopropene and 10 ml of 1-vinylimidazole separately, pour into a 50 ml beaker, stir rapidly so that the solution is mixed evenly, stand still for the reaction, whereby the reaction solution containing the carbon dots is obtained; (2) After naturally cooling the reaction solution obtained in step (1), centrifuging for 10 minutes at 8000 rpm in a high-speed centrifuge to obtain a supernatant, then filtering the supernatant with a 0.22 µm microporous filter membrane; The filtrate is dialyzed by means of a dialysis bag with a molecular weight limit of 500 Da for 48 hours and then freeze-dried to obtain the carbon point powder, and finally a part of the carbon point powder is dispersed each with ultrapure water and ethanol to obtain a carbon point dispersion liquid, store at 4 ° C.
    Example 3 The method for making carbon dots with bromopropene and 1-vinylimidazole, comprising the following steps: (1) separately measuring 2 ml of bromopropene and 6 ml of 1-vinylimidazole, pouring into a 50 ml beaker, stirring rapidly, making the solution uniform is mixed, standing still for the reaction, thereby obtaining the reaction solution containing carbon dots; (2) After naturally cooling the reaction solution obtained in step (1), centrifuging for 10 minutes at 8000 rpm in a high-speed centrifuge to obtain a supernatant, then filtering the supernatant with a 0.22 µm microporous filter membrane; The filtrate is dialyzed by means of a dialysis bag with a molecular weight limit of 500 Da for 48 hours and then freeze-dried, whereby the carbon point powder is obtained, and finally a part of the carbon point powder is dispersed each with ultrapure water and ethanol, whereby a
    Carbon point dispersion liquid is obtained, store at 4 ° C.
    Characterization of the obtained carbon dots: Fig. 1 is a transmission electron microscope picture of carbon dots produced by the present invention. From the morphological analysis of the carbon dots in FIG. 1, it can be seen that the carbon dots are spherical and of uniform size.
    Fig. 2 is a histogram of the particle size distribution of carbon dots produced by the present invention. As can be seen from the figure, the average particle size of carbon dots is 11.6 nm and the particle size distribution range is from 8 to 14 nm.
    Fig. 3 is a UV absorption spectrum of carbon dots produced by the present invention. The carbon dots have an apparent absorption peak around 310 nm which is a transition of the core carbon from n-n.
    Fig. 4 is an infrared absorption spectrum of carbon dots produced by the present invention. The peak at 3434 cmt is due to the stretching vibration of NH, and the peak at 3073 cmt is due to the unsaturated CH stretching, the peak at 1647 cm- is due to C = C stretching, the peaks at 1550 and 1427 cmt in each case due to the stretching vibration of C = N and CN, and the peak at 1163 cm! is due to C-Br stretching vibration, the peak at 948 cmt is the bending vibration of C-H out of plane on the ring.
    Fig. 5 is an emission spectrum of the carbon dots produced by the present invention at various excitation wavelengths, the maximum excitation wavelength is 380 nm, and the corresponding emission wavelength is 466 nm, under ultraviolet excitation it shows an intense blue fluorescence and shows as an excitation-dependent fluorescence. With increasing excitation wavelength, the emission shifts to red.
    Quantum yield analysis: The relative quantum yields of the carbon dots produced in Examples 1 to 3 of the present invention are measured, using quinine sulfate as a comparison, where it is dissolved in a 0.1 M H2S04 solution, the fluorescence quantum yield at an excitation wavelength of 360 nm 54 % is. The specific procedure is as follows: first setting a certain low concentration of carbon point solution and quinine sulfate solution, then measuring their UV-Vis spectral absorption value at 360 nm, regulating the concentration so that the absorption value is less than 0.05, and measuring the respective peak area of the fluorescence emission spectrum on the fluorescence spectrometer (FIGS. 6 and 7). After repeatedly measuring five different concentrations, each of the peak area of the fluorescence spectrum and the absorption value of the UV-Vis spectrum are obtained, and the slope can be obtained by graph. The relative
    The quantum yield can be determined using the following equation: Dx = Ost (Ix / Ist) (Tk / Nat) ”Where ® represents the quantum yield, n the correlation coefficient of the solvent (1.36 in anhydrous ethanol and 1.33 in 0.1 M diluted Sulfuric acid solution), I represents the peak area of the fluorescence emission spectrum and the slope ratio of the corresponding absorption value of the UV-Vis spectrum; Index "xn" and "st" show the carbon point sample and the fluorescent reference standard, respectively, and the results are shown in Table 1.
    Table 1. Quantum yield measurement data of carbon dots pee ee a ire The results show that the methods of Examples 1 to 3 of the present invention can obtain carbon dots having a particle size of 8 to 14 nm and in which the quantum yield is 17%. The process can react directly at room temperature (5-40 ° C) without additional energy consumption, this is green and environmentally friendly and the
    Response time is short.
    On condition that the reaction system is larger than 30 ml, the carbon dots are generated by reaction within seconds.
    The response time is reduced as the volume of the system increases.
    Accordingly, the object of the present invention can be achieved by setting the response time to be more than 1 second.
    A new synthesis method for carbon point synthesis has been found.
    Example 4 The method of making carbon dots with bromopropene and 1-methylimidazole comprising the following steps:
    (1) measuring 5 ml of bromopropene and 5 ml of 1-methylimidazole separately, pouring into a 50 ml beaker, stirring rapidly to mix the solution evenly, standing still for the reaction to obtain the reaction solution containing carbon dots; (2) After naturally cooling the reaction solution obtained in step (1), centrifuging for 10 minutes at 8000 rpm in a high-speed centrifuge to obtain a supernatant, then filtering the supernatant with a 0.22 µm microporous filter membrane; The filtrate is dialyzed by means of a dialysis bag with a molecular weight limit of 500 Da for 48 hours and then freeze-dried, whereby the carbon point powder is obtained, and finally a part of the carbon point powder is dispersed each with ultrapure water and ethanol, whereby a carbon point dispersion liquid is obtained, store at 4 ° C.
    In this embodiment, the reaction is possible if the reaction time is set to more than 1 s, the temperature is set in the range of up to 40 ° C. and the volume ratio of bromopropene to 1-5 methylimidazole is set to 1: 1 to 1: 3. Characterizing the Prepared Carbon Dots: Figure 8 is a UV absorption spectrum of carbon dots produced in this example. The carbon dots have an apparent absorption peak at around 280 nm, which is a transition of the core carbon from m-m *.
    Fig. 9 is an emission spectrum at various excitation wavelengths of carbon dots generated in this example. The maximum excitation wavelength is 370 nm and the corresponding emission wavelength is 433 nm, which shows a strong blue fluorescence under ultraviolet excitation.
    The quantum yield of the carbon dots produced in this example corresponds to that in Example 1, which indicates that bromopropene and 1-vinylimidazole, 1-methylimidazole or other imidazole compounds can be used to produce carbon dots. The above-mentioned examples are only preferred examples for fully illustrating the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions or changes made by those skilled in the art based on the present invention are all encompassed in
    Scope of the present invention.
    The scope of the present invention is determined by the claims.
    权利要求:
    Claims (10)
    [1]
    1. A method for producing carbon dots with bromopropene and imidazole compounds, characterized in that the bromopropene and imidazole compounds react immediately after mixing to produce carbon dots.
    [2]
    2. The method according to claim 1, characterized in that the imidazole compound is at least one of 1-vinylimidazole or 1-methylimidazole.
    [3]
    3. The method according to claim 1, characterized in that the bromopropene and imidazole compounds are mixed in a volume ratio of 1: 1 to 1: 3.
    [4]
    4. The method according to claim 1, characterized in that the reaction temperature is 5 to 40 ° C.
    [5]
    5. The method according to claim 1, characterized in that the mixing is carried out in the manner of stirring.
    [6]
    6. The method according to claim 1, characterized in that the reaction time is at least 1 s.
    [7]
    7. The method according to any one of claims 1 to 6, characterized in that after the reaction, carbon points are further collected, in particular cooling the reaction solution, centrifuging, filtering, dialyzing and freeze-drying, whereby the carbon point powder is obtained.
    [8]
    8. The method according to claim 7, characterized in that centrifuging at 8000 rpm for 10 to 20 minutes,
    filtering with a 0.22 µm microporous filter membrane and dialyzing with a dialysis bag with a molecular weight limit of 500 Da for 24 to 48 hours.
    [9]
    9. carbon point produced by the method according to any one of claims 1-8.
    [10]
    10. carbon point according to claim 9, characterized in that the average particle size is 11.6 nm and the particle size distribution range is 8 to 14 nm.
    类似技术:
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    同族专利:
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    法律状态:
    2021-04-23| FG| Patent granted|Effective date: 20210419 |
    优先权:
    申请号 | 申请日 | 专利标题
    CN201910664334.1A|CN110229665B|2019-07-23|2019-07-23|Method for preparing carbon dots by utilizing bromopropylene and imidazole compounds and product|
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