Polymer fluorescent carbon dots with PBAT as carbon source, preparation method thereof and application thereof in detection of iron ions
The preparation of polymeric fluorescent carbon dots using PBAT as a carbon source via a hydrothermal method solves the problem of preparing high-purity and non-toxic carbon dots in existing technologies, and achieves high-sensitivity detection of iron ions, making it suitable for health monitoring and drug development.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- LIAONING UNIVERSITY
- Filing Date
- 2024-11-11
- Publication Date
- 2026-06-16
AI Technical Summary
Existing technologies are difficult to effectively utilize plastics to prepare high-purity, non-toxic carbon dots with high fluorescence properties, and lack sensitivity and selectivity for iron ion detection.
A hydrothermal method was used to prepare polymeric fluorescent carbon dots using PBAT as the carbon source through a multi-step process. These carbon dots were then applied to the detection of iron ions, taking advantage of their blue-green fluorescence properties and selective quenching effect on iron ions.
The prepared carbon dots have high purity and stable fluorescence properties, and can be used as fluorescent probes for quantitative detection of iron ions, providing the possibility of trace detection and supporting drug development and health monitoring.
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Figure CN119463861B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of fluorescent carbon quantum dot technology, and particularly relates to a polymeric fluorescent carbon dot with PBAT as the carbon source, its preparation method, and its application in the detection of iron ions. Background Technology
[0002] With the increasing prominence of environmental issues and the demand for novel functional materials, the preparation of carbon dots using plastics is gradually attracting widespread attention as an innovative approach. This invention reduces reliance on traditional carbon sources, providing a new sustainable resource for carbon dot preparation. Using plastics as raw materials solves the environmental pollution problem caused by plastics, converting them into carbon dots and achieving waste recycling, which aligns with the concept of sustainable development. The preparation process is relatively simple, highly operable, and requires no toxic reagents. 3+ Iron is a form of iron found in the human body, and its content level can reflect a person's health status. Trace detection can help people understand their own iron intake, absorption, and metabolism, providing guidance for a balanced diet and iron supplementation, and helping to prevent iron deficiency or iron overload. 3+ Trace detection can aid in the diagnosis of liver diseases, anemia, etc., providing a basis for treatment. In the development of certain drugs, it is also necessary to understand the effect of drugs on the body's iron metabolism. Trace detection of ferric iron can provide data support for the evaluation of drug safety and efficacy, helping researchers better understand the drug's mechanism of action and potential side effects. This study used a copolymer of butylene adipate and butylene terephthalate (PBAT) as a carbon source to synthesize blue-green fluorescent carbon dots via a hydrothermal method, which are used to detect trace amounts of ferric iron. 3+ It exhibits excellent selectivity and sensitivity.
[0003] Fluorescent carbon quantum dots are a promising nanomaterial with good biocompatibility, high water solubility, and low toxicity, and are widely used in the field of trace detection. Summary of the Invention
[0004] To address the shortcomings of existing technologies, this invention utilizes a hydrothermal method to prepare high-purity carbon quantum dots with high fluorescence properties in one step, and verifies that they can be widely used as fluorescence detectors for detecting iron ions.
[0005] To achieve the above objectives, the technical solution of the present invention is as follows: a polymeric fluorescent carbon dot using PBAT as a carbon source, the preparation method comprising the following steps:
[0006] Step 1: Place PBAT in an open ceramic crucible and heat it to form a dark brown oxide product for later use;
[0007] Step 2: Transfer the product obtained in Step 1 to a reaction vessel containing H2O2 solution;
[0008] Step 3: Place the above reaction vessel in an oven for hydrothermal treatment to obtain a dark brown dispersion;
[0009] Step 4: Centrifuge the above dispersion and collect the supernatant;
[0010] Step 5: Place the obtained solution into a dialysis bag and dialyze it in ultrapure water to remove impurities, obtaining a pale yellow solution;
[0011] Step 6: Place the obtained solution in a freeze dryer and freeze dry to obtain polymeric fluorescent carbon dots with PBAT as the carbon source.
[0012] In the above-mentioned polymeric fluorescent carbon dot with PBAT as the carbon source, step 1 involves heating in air at 330°C for 2 hours.
[0013] In the above-mentioned polymeric fluorescent carbon dot with PBAT as the carbon source, in step 2, the mass fraction of H2O2 solution is 4wt%, and the product obtained in step 1:H2O2 solution = 1g:60mL.
[0014] In the above-mentioned polymeric fluorescent carbon dot with PBAT as the carbon source, the hydrothermal treatment in step 3 is a hydrothermal treatment at 180°C for 6 hours.
[0015] In step 4 of the above-mentioned polymeric fluorescent carbon dot using PBAT as a carbon source, the centrifugation is performed at 10,000 rpm for 30 minutes.
[0016] In step 5 of the aforementioned polymeric fluorescent carbon dot using PBAT as a carbon source, the dialysis bag has a specification of 500 Da, and the amount of ultrapure water used is 3 L.
[0017] In step 6 of the above-mentioned polymeric fluorescent carbon dot using PBAT as a carbon source, the freeze-drying temperature is -45℃ and the time is 24h.
[0018] The above-mentioned application of polymeric fluorescent carbon dots with PBAT as a carbon source as fluorescent probes in the detection of iron ions.
[0019] The above application includes the following steps:
[0020] Step 1: Take 0.2 ml of solution from the test solution containing different concentrations of iron ions (0-67.64 μM), add 0.6 ml of water, and then add 0.2 ml of the above-mentioned fluorescent probe at a concentration of 0.1 mg / mL. After mixing evenly, react for 10 min.
[0021] Step 2: Place the mixed solution obtained in Step 1 into a fluorescence spectrometer, select 330 nm as the excitation wavelength, set the spectral range to 330-600 nm, and after obtaining the complete fluorescence spectrum, read the fluorescence intensity value I at 451 nm.
[0022] Step 3: Measure 0.8 ml of ultrapure water and add it to 0.2 ml of the above fluorescent probe at a concentration of 0.1 mg / mL. After mixing thoroughly, react for 10 min.
[0023] Step 4: Place the mixed solution obtained in Step 3 into a fluorescence spectrometer, select 330 nm as the excitation wavelength, and set the spectral range to 330–600 nm. After obtaining the complete fluorescence spectrum, read the fluorescence intensity value I0 at 451 nm.
[0024] Step 5: Calculate the value of (I-I0) / I0, and plot (I-I0) / I0 and Fe. 3+ The standard curve is used to calculate the Fe content in the test solution. 3+ The concentration.
[0025] Fe 3+ The linear equation for the fluorescence intensity of carbon dots and their concentration is y = 0.01252x - 0.16511, R0 2 =0.995.
[0026] Following steps 1-5, take samples containing Fe of unknown concentration. 3+ The solution was analyzed to obtain fluorescence intensity values I and I0, and Fe was calculated based on the linear equation. 3+ The concentration.
[0027] Furthermore, in the above applications, the Fe 3+ The method for plotting the standard curve is as follows: Take 200 μL of Fe with concentrations ranging from 0 to 67.64 μmol / L. 3+ The standard solution was prepared by adding 200 μL of the above-mentioned fluorescent carbon dot solution (0.1 mg / mL) and 600 μL of water to each solution. After thorough mixing, the mixture was allowed to react for 1 min to obtain a gradient concentration of Fe. 3+ Fluorescent carbon dot mixed solutions were placed in a fluorescence spectrometer, with 330 nm as the excitation wavelength and the spectral range set to 330 nm-600 nm. After obtaining the complete fluorescence spectrum, the fluorescence intensity value I at 451 nm was read. (The last part, "Fe," appears to be an incomplete sentence or fragment and doesn't translate directly.) 3+ Plot the Fe concentration on the x-axis and the value of (I-I0) / I0 on the y-axis. 3+ The standard curve.
[0028] The optimal excitation wavelength of the carbon quantum dots is 330 nm, the optimal emission wavelength is 451 nm, and they exhibit blue-green fluorescence under a 365 nm ultraviolet lamp.
[0029] Compared with the prior art, the present invention has the following beneficial technical effects:
[0030] This invention utilizes a hydrothermal method to prepare fluorescent carbon quantum dots in a one-step process. These quantum dots possess high purity, stable fluorescence properties, and are non-toxic. Detection experiments show that the prepared carbon quantum dots can be used as a fluorescence probe for the quantitative detection of iron ions, and hold promise as a fluorescent probe for iron ion detection. Attached Figure Description
[0031] Figure 1 This is a schematic diagram illustrating the synthesis of the fluorescent carbon dots prepared in this invention.
[0032] Figure 2 This is a transmission electron microscope image of the carbon quantum dots prepared in this invention;
[0033] Figure 3 The optimal excitation spectrum, optimal emission spectrum, and ultraviolet spectrum of the carbon quantum dots prepared in this invention are shown.
[0034] Figure 4 The fluorescence spectra of the carbon quantum dots prepared in this invention at different excitation wavelengths are shown.
[0035] Figure 5 The fluorescence intensity diagram of the time stability of the carbon quantum dots prepared in this invention;
[0036] Figure 6 The graph shows the fluorescence intensity variation of the carbon quantum dots prepared in this invention under different ions.
[0037] Figure 7 Different concentrations of Fe were added to the carbon quantum dots prepared in this invention. 3+ Graph showing changes in fluorescence intensity after solution treatment;
[0038] Figure 8 Fluorescent carbon dots prepared for this invention are used as probes for Fe 3+ Standard curve plot;
[0039] Figure 9 The carbon quantum dots prepared in this invention and in Fe 3+ Linearity graph for solution concentrations in the range of 32.89–47.09 μM / L.
[0040] Specific implementation methods
[0041] The present invention will be further illustrated by specific examples below. The present invention is not limited to the embodiments described, and minor variations may be made without departing from the scope thereof.
[0042] Example 1: A method for preparing polymeric fluorescent carbon dots using PBAT as a carbon source
[0043] Includes the following steps:
[0044] Step 1: Weigh 5g of PBAT, place it in an open ceramic crucible, and heat it in air at 330°C for 2 hours to form a dark brown oxide product for later use.
[0045] Step 2: Weigh 0.5g of the product obtained in Step 1 and transfer it to a 30mL reactor containing a 4wt% H2O2 solution; the reactor capacity is 75mL.
[0046] Step 3: Place the above reaction vessel in an oven and perform hydrothermal treatment at 180℃ for 6 hours to obtain a dark brown dispersion;
[0047] Step 4: Centrifuge the above dispersion at 10,000 rpm for 30 min and collect the supernatant;
[0048] Step 5: Place the obtained solution into a 500 Da dialysis bag and pour it into 3 L of ultrapure water for dialysis to remove impurities, obtaining a pale yellow solution.
[0049] Step 6: Place the obtained solution in a freeze dryer and freeze dry to obtain polymeric fluorescent carbon dots with PBAT as the carbon source.
[0050] Example 2: Characterization of polymeric fluorescent carbon dots using PBAT as the carbon source
[0051] The specific characterization results are as follows:
[0052] (1) Transmission electron microscopy (TEM) images: The polymeric fluorescent carbon dots prepared in Example 1 above using PBAT as the carbon source were characterized by TEM images, showing that their size is approximately 4 nm (e.g., ...). Figure 2 (As shown).
[0053] (2) The optimal excitation and emission wavelengths of the polymeric fluorescent carbon dot solution using PBAT as the carbon source are 330 nm and 451 nm, respectively (e.g., Figure 3 As shown in the figure, it exhibits blue-green fluorescence under a 365 nm UV lamp; the UV absorption spectrum shows an absorption peak near 238 nm, which may originate from the π-π* transition of polyaromatic chromophores. Studies of its fluorescence spectra at different excitation wavelengths (330–380 nm) revealed (as shown in the figure)... Figure 4 As shown in the figure, it exhibits excitation-independent fluorescence emission properties, which is related to the uniform size distribution and surface defects of the synthesized polymeric fluorescent carbon dots with PBAT as the carbon source.
[0054] (4) The study on the fluorescence stability of polymeric fluorescent carbon dots using PBAT as the carbon source shows that the fluorescence intensity of carbon quantum dots was tested under different metal ions, different 330nm UV lamp irradiation times, and different salt ion intensities. For example... Figure 6As shown, the PBAT-based polymeric fluorescent carbon dots exhibit a quenching effect only on iron ions in aqueous solutions of different metal ions; other metal ions have almost no effect on the fluorescence intensity of the PBAT-based polymeric fluorescent carbon dots. This indicates that the PBAT-based polymeric fluorescent carbon dots can be used as a fluorescent probe for detecting iron ions.
[0055] The fluorescence intensity of the carbon quantum dots remained almost unchanged under different UV irradiation times, indicating that the aforementioned carbon quantum dots have good photobleaching resistance. Figure 5 (As shown).
[0056] Example 3: Detection of iron ions using polymeric fluorescent carbon dots with PBAT as the carbon source as fluorescent probes.
[0057] The specific testing method includes the following steps:
[0058] Step 1: Take 0.2 ml of solution from the test solution containing different concentrations of iron ions (0-67.64 μM), add 0.6 ml of water, add 0.2 ml of 0.1 mg / mL carbon quantum dot solution fluorescent probe, and after mixing evenly, react for 10 min.
[0059] Step 2: Place the mixed solution obtained in Step 1 into a fluorescence spectrometer, select 330 nm as the excitation wavelength, set the spectral range to 330-600 nm, and after obtaining the complete fluorescence spectrum, read the fluorescence intensity value I at 451 nm.
[0060] Step 3: Measure 0.8 ml of ultrapure water and add it to 0.2 ml of the above-mentioned 0.1 mg / mL carbon dot solution fluorescent probe. After mixing evenly, react for 10 min.
[0061] Step 4: Place the mixed solution obtained in Step 3 into a fluorescence spectrometer, select 330 nm as the excitation wavelength, and set the spectral range to 330–600 nm. After obtaining the complete fluorescence spectrum, read the fluorescence intensity value I0 at 451 nm. Comparing I and I0 proves that the fluorescent probe can be effectively quenched by iron ions.
[0062] Step 5: Calculate the value of (I-I0) / I0, and plot (I-I0) / I0 and Fe. 3+ The standard curve is used to calculate the Fe content in the test solution. 3+ The concentration.
[0063] The fluorescence intensity and Fe of polymeric fluorescent carbon dots with PBAT as the carbon source 3+ Concentration relationship (e.g.) Figure 7 (As shown). When Fe is added to a carbon quantum dot solution... 3+ Fe solution 3+The higher the concentration, the lower the fluorescence intensity. 200 μL of Fe was taken at concentrations ranging from 0 to 67.64 μmol / L. 3+ The standard solution was prepared by adding 200 μL of the above-mentioned fluorescent carbon dot solution (0.1 mg / mL) and 600 μL of water to each solution. After thorough mixing, the mixture was allowed to react for 1 min to obtain a gradient concentration of Fe. 3+ Fluorescent carbon dot mixed solutions were placed in a fluorescence spectrometer, with 330 nm as the excitation wavelength and the spectral range set to 330 nm-600 nm. After obtaining the complete fluorescence spectrum, the fluorescence intensity value I at 451 nm was read. (The last part, "Fe," appears to be an incomplete sentence or fragment and doesn't translate directly.) 3+ Plot the Fe concentration on the x-axis and the value of (I-I0) / I0 on the y-axis. 3+ Standard curve ( Figure 8 and Figure 9 ). Explanation of Fe 3+ There is a good linear relationship between the fluorescence intensity of carbon dots and (e.g.) Figure 9 As shown), y = 0.01252x - 0.16511, R 2 =0.995, which allows for the quantitative detection of ferric ions.
[0064] In summary, the polymeric fluorescent carbon dots prepared by the hydrothermal method using PBAT as the carbon source in this invention possess high purity, stable fluorescence properties, and are non-toxic. Detection experiments show that the prepared carbon quantum dots can be used as fluorescent probes for the quantitative detection of iron ions.
Claims
1. An application of polymeric fluorescent carbon dots using PBAT as a carbon source as fluorescent probes in the detection of iron ions, characterized in that, The method for preparing polymeric fluorescent carbon dots using PBAT as a carbon source includes the following steps: Step 1: Place PBAT in an open ceramic crucible and heat in air at 330 °C for 2 hours to form a dark brown oxide product for later use. Step 2: Transfer the product obtained in Step 1 to a reactor containing a 4 wt% H₂O₂ solution; the ratio of product obtained in Step 1 to H₂O₂ solution is 1 g: 60 mL. Step 3: Place the above reaction vessel in an oven for hydrothermal treatment at 180 °C for 6 h to obtain a dark brown dispersion; Step 4: Centrifuge the above dispersion at 10,000 rpm for 30 min and collect the supernatant; Step 5: Place the obtained solution into a dialysis bag and dialyze it in ultrapure water to remove impurities, obtaining a pale yellow solution; Step 6: Place the obtained solution in a freeze dryer and freeze dry to obtain polymeric fluorescent carbon dots with PBAT as the carbon source; The PBAT is a copolymer of butylene adipate and butylene terephthalate.
2. The application according to claim 1, characterized in that, In step 5, the dialysis bag has a specification of 500 Da, and the amount of ultrapure water used is 3 L.
3. The application according to claim 1, characterized in that, In step 6, the freeze-drying temperature is -45℃ and the time is 24 hours.
4. The application according to any one of claims 1-3, characterized in that, Includes the following steps: Step 1: Take 0.2 ml of solution from the test solution containing iron ions of different concentrations (0-67.64 μM), add 0.6 ml of water, and then add 0.2 ml of a 0.1 mg / mL solution of polymeric fluorescent carbon dots with PBAT as the carbon source as described in any one of claims 1-3. After mixing evenly, react for 10 min. Step 2: Place the mixed solution obtained in Step 1 into a fluorescence spectrometer, select 330 nm as the excitation wavelength, set the spectral range to 330~600 nm, and after obtaining the complete fluorescence spectrum, read the fluorescence intensity value I at 451 nm. Step 3: Measure 0.8 ml of ultrapure water and add it to 0.2 ml of a 0.1 mg / mL solution of polymeric fluorescent carbon dots with PBAT as the carbon source as described in any one of claims 1-3. After mixing evenly, react for 10 min. Step 4: Place the mixed solution obtained in Step 3 into a fluorescence spectrometer, select 330 nm as the excitation wavelength, set the spectral range to 330~600 nm, and after obtaining the complete fluorescence spectrum, read the fluorescence intensity value I0 at 451 nm. Step 5: Calculate the value of (I-I0) / I0, and plot (I-I0) / I0 and Fe. 3+ The standard curve is used to calculate the Fe content in the test solution. 3+ The concentration.
5. The application according to claim 4, characterized in that, The Fe 3+ The standard curve is plotted as follows: Take 200 μL of Fe with concentrations ranging from 0 to 67.64 μmol / L. 3+ The standard solution was prepared by adding 200 μL of the above-mentioned fluorescent carbon dot solution (0.1 mg / mL) and 600 μL of water to each solution. After thorough mixing, the mixture was allowed to react for 1 min to obtain a gradient concentration of Fe. 3+ Fluorescent carbon dot mixed solutions were placed in a fluorescence spectrometer, with 330 nm as the excitation wavelength and the spectral range set to 330 nm-600 nm. After obtaining the complete fluorescence spectrum, the fluorescence intensity value I at 451 nm was read. (The last part, "Fe," appears to be an incomplete sentence or fragment and doesn't translate directly.) 3+ Plot the Fe concentration on the x-axis and the value of (I-I0) / I0 on the y-axis. 3+ The standard curve.