Beta-cyclodextrin sulfur quantum dot for simultaneously detecting curcumin and Fe < 3 + > and preparation method
Preparation of spherical β-cyclodextrin sulfur quantum dots through high-temperature and high-pressure reactors solves the problem of long preparation time and achieves fast and accurate fluorescence sensing analysis, especially when detecting curcumin and Fe3+, which significantly improves the detection efficiency and selectivity, avoiding the limitations of expensive equipment and cumbersome operation.
Patent Information
- Application Number
- CN202411417676.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-11
- Publication Date
- 2025-01-10
AI Technical Summary
In the prior art, the preparation time of β-cyclodextrin sulfur quantum dots is limited, which limits its wide application in fluorescence sensing analysis, especially when detecting curcumin and Fe3+, the equipment is expensive, cumbersome and susceptible to interference. .
The preparation time was shortened by a high-temperature autoclave for the preparation of β-cyclodextrin sulfur quantum dots. The preparation time was shortened by dialysis purification and Freeze-drying to obtain spherical quantum dots for ratio fluorescence detection of curcumin and Fe3+.
The preparation time of β-cyclodextrin sulfur quantum dots is significantly shortened, the synthesis efficiency is improved, and the accurate quantity detection of curcumin and Fe3+ is achieved, and it has good anti-interference ability and selectivity.
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Figure CN119286503A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of fluorescence sensing analysis, and specifically relates to a method for simultaneously detecting curcumin and Fe 3+ β-cyclodextrin sulfur quantum dots and preparation method thereof. Background Art
[0002] Curcumin (Cur) is a polyphenolic pigment extracted from the root of the plant turmeric, commonly used in cosmetics and spices. Many studies have shown that excessive use of curcumin may inactivate human DNA, lead to a decrease in intracellular ATP levels, and cause irreversible effects such as tissue necrosis. Given the increasing application of curcumin in various fields, quantitative detection of the content of curcumin in related products is of great significance.
[0003] At present, the methods for quantitative detection of curcumin include capillary electrophoresis, electrochemical method, thin layer chromatography, UV-visible spectrophotometry, etc. However, expensive equipment, cumbersome sample pretreatment, complex operation and long detection cycle limit its wide application. At the same time, fluorescence spectroscopy has attracted widespread attention due to its advantages such as convenient operation, high sensitivity and fast response speed. In addition, detection based on a single fluorescence signal is more likely to be interfered by other factors, and ratio fluorescence sensing is more accurate and effective. Sulfur quantum dots, as emerging non-metallic quantum dots, have been applied in the fields of fluorescence sensing and biological antibacterial based on their good photoluminescence and unique antibacterial properties. The reported preparation time of β-cyclodextrin sulfur quantum dots using sublimated sulfur powder as the sulfur source is about 144 h, which seriously limits its wide application. Summary of the invention
[0004] Aiming at the problem that the preparation time of β-cyclodextrin sulfur quantum dots using sublimated sulfur powder as sulfur source is long, the present invention provides a method for simultaneously detecting curcumin and Fe 3+ β-cyclodextrin sulfur quantum dots and preparation method thereof.
[0005] In order to achieve the above object, the present invention adopts the following technical solutions: A method for simultaneous detection of curcumin and Fe 3+ The β-cyclodextrin sulfur quantum dots have a spherical structure and a particle size distribution between 0.55 nm and 1.25 nm.
[0006] Furthermore, the lattice spacing of the β-cyclodextrin sulfur quantum dots is 0.214 nm, and the average particle size is 0.9±0.1 nm.
[0007] Furthermore, the optimal excitation light of the β-cyclodextrin sulfur quantum dots is at 320 nm, and the maximum emission peak is at 420 nm.
[0008] Furthermore, the linear range of the β-cyclodextrin sulfur quantum dots for detecting curcumin is 0.50-90 μM, and the detection sensitivity is 23 nM.
[0009] Further, the β-cyclodextrin sulfur quantum dots detect Fe in the curcumin system 3+ The linear range is 0.80~100μM, and the detection sensitivity is 0.58 μM.
[0010] A method for simultaneous detection of curcumin and Fe 3+ The preparation method of β-cyclodextrin sulfur quantum dots comprises the following steps: adding sodium hydroxide, sublimated sulfur powder and β-cyclodextrin into ultrapure water, heating and stirring until completely dissolved, transferring the mixed solution into a polytetrafluoroethylene reactor for high temperature and high pressure reaction, and obtaining the β-cyclodextrin sulfur quantum dots after purification by dialysis and freeze drying.
[0011] Furthermore, the mass ratio of the sublimated sulfur powder to β-cyclodextrin is (1-1.5):(1-1.3).
[0012] Furthermore, the temperature of the heating and stirring is 50°C and the time is 30 min; the specific steps of the dialysis purification are: dialysis in a dialysis bag with a molecular weight cutoff of 3500 Da for 12 to 16 hours; the freeze-drying time is: 24 hours; the temperature of the high temperature and high pressure reaction is 170°C and the time is 6 hours.
[0013] The β-cyclodextrin sulfur quantum dots prepared by the above preparation method are 3+ Applications in fluorescence sensing.
[0014] Further, it is used for the detection of curcumin in beverages.
[0015] Compared with the prior art, the present invention has the following advantages: The β-cyclodextrin sulfur quantum dots provided by the present invention are rapidly prepared in a reactor in 6 h, which significantly improves the synthesis efficiency compared with the reported preparation method of β-cyclodextrin sulfur quantum dots (144 h). 3+ It can cause the ratiometric fluorescence change of β-cyclodextrin sulfur quantum dots, realizing the fluorescence of curcumin and Fe 3+ Quantitative detection of .
[0016] Here, we used a reactor to prepare it in 6 h, which significantly shortened the synthesis time. And the rapidly prepared β-cyclodextrin sulfur quantum dots were used for ratiometric fluorescence detection of curcumin and Fe 3+ . BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Figure 1 This is a TEM image of the β-cyclodextrin sulfur quantum dots prepared in Example 1 of the present invention.
[0018] Figure 2 This is the XPS graph of β-cyclodextrin sulfur quantum dots prepared in Example 1 of the present invention.
[0019] Figure 3 This is a fluorescence emission spectrum of β-cyclodextrin sulfur quantum dots prepared in Example 1 of the present invention.
[0020] Figure 4 This is a fluorescence emission spectrum of β-cyclodextrin sulfur quantum dots prepared in Example 1 of the present invention for detecting curcumin.
[0021] Figure 5 This is a linear relationship diagram between curcumin concentration and the fluorescence intensity change of β-cyclodextrin sulfur quantum dots.
[0022] Figure 6 β-cyclodextrin sulfur quantum dots and curcumin sensing system for Fe detection 3+ Fluorescence emission spectrum of .
[0023] Figure 7 Fe 3+ Linear relationship between concentration and fluorescence intensity change of β-cyclodextrin sulfur quantum dots and curcumin sensing system.
[0024] Figure 8 Schematic diagram of the selectivity and interference evaluation results of the fluorescence sensing system. DETAILED DESCRIPTION
[0025] In order to gain a deeper understanding of the present invention, we will provide a comprehensive and detailed description of the present invention. However, the present invention has multiple implementations and is not limited to the specific examples listed herein. The presentation of these examples is intended to deepen the comprehensive understanding of the disclosure of the present invention.
[0026] 1. Preparation of Sulfur Quantum Dots Example 1
[0027] Dissolve 0.80 g of sodium hydroxide in 25 mL of ultrapure water, add 0.30 g of β-cyclodextrin, stir to obtain a clear solution, add 0.30 g of sublimated sulfur powder, and finally heat and stir for 30 min until the sulfur powder is dissolved. Move the above solution to the reactor and react in an oven (170°C) for 6 h to obtain a light yellow sulfur quantum dot solution. Use a dialysis bag with a molecular weight cutoff of 3500 Da to dialyze and purify the sulfur quantum dot stock solution obtained by the above reaction for 12 to 16 h to obtain purified β-cyclodextrin sulfur quantum dots, which are freeze-dried for 24 h to obtain light yellow cotton-like β-cyclodextrin sulfur quantum dots.
[0028] Characterization test: such as Figure 1The results show that the β-cyclodextrin sulfur quantum dots prepared by the above method present small-sized, well-dispersed spherical particles. The lattice spacing is 0.214 nm, and the particle size distribution is between 0.55 nm and 1.25 nm, with an average particle size of 0.9±0.1 nm. Figure 2 As shown in the figure, β-cyclodextrin sulfur quantum dots mainly contain three elements: S, C, and O. The two peaks at 161.58 eV and 162.68 eV in the high-resolution X-ray photoelectron spectrum of sulfur are characteristic peaks of atomic sulfur, and the peaks at 166.78 eV, 167.68 eV, and 168.78 eV are signal peaks of sulfur oxide species, indicating that β-cyclodextrin sulfur quantum dots are mainly composed of atomic sulfur and sulfonate and sulfite groups on their surfaces. Figure 3 As shown in Figure 2, the maximum emission peak of the β-cyclodextrin sulfur quantum dots prepared by the above method is located at 420 nm under the optimal excitation at 320 nm. 2 SO 4 ) solution as a reference, the quantum yield of the sulfur quantum dots is 0.068.
[0029] 2. Ratiometric Fluorescence Detection of Curcumin and Fe by β-cyclodextrin Sulfur Quantum Dots 3+ Applications Example 2
[0030] Different concentrations of curcumin were added to the β-cyclodextrin sulfur quantum dots prepared in Example 1, and the mixture was reacted at room temperature for 2 min. The fluorescence spectrum thereof was tested under excitation at 320 nm.
[0031] Depend on Figure 4 It can be seen that with the continuous addition of curcumin, the fluorescence emission of the β-cyclodextrin sulfur quantum dots prepared in Example 1 at 420 nm is gradually quenched. Figure 5 It can be seen that the linear range of the β-cyclodextrin sulfur quantum dots prepared in Example 1 for detecting curcumin is 0.50~90 μM, and the detection sensitivity is 23 nM.
[0032] Example 3
[0033] A certain concentration of curcumin (90 μM) was added to the β-cyclodextrin sulfur quantum dots prepared in Example 1, and then different volumes of Fe 3+ The standard solution (final concentration was 100 μM) was allowed to stand for 2 min, and then the fluorescence spectrum of the sensing solution was tested under 320 nm excitation.
[0034] Depend on Figure 6 It can be seen that with the increase of Fe 3+ With the continuous addition of , the ratiometric fluorescence phenomenon of β-cyclodextrin sulfur quantum dots gradually recovered. Figure 7 It can be seen that the β-cyclodextrin sulfur quantum dots and curcumin sensing system detects Fe 3+ The linear range of the assay was 0.80-100 μM, and the detection sensitivity was 0.58 μM.
[0035] Example 4
[0036] The health product curcumin capsule powder was dissolved in methanol and placed in an ultrasonic bath for 10 min, and the curcumin in the health product curcumin capsule was detected according to the steps described in Example 2. Subsequently, different concentrations of curcumin were added to the sample solution, and a spike recovery test was performed. The results are shown in Table 1. The spike recovery rate of curcumin in the health product curcumin capsule sample was 97.0%~105%, and the relative standard deviation was less than 2.02%. The above results show that the β-cyclodextrin sulfur quantum dots can be used for the analysis and detection of curcumin in actual samples.
[0037] Example 5
[0038] The tap water was centrifuged and filtered with a 0.22 μmol / L microporous membrane to obtain a tap water sample. Fe 3+ Standard solution, so that the concentration of Fe in the sensing system 3+ The concentration of Fe in tap water samples was 2.00, 4.50, and 10.0 µmol / L, and the spike recovery experiment was performed. The results are shown in Table 2. 3+ The recovery rate was between 98.7% and 105%, and the RSD was between 1.68% and 2.13%. The β-cyclodextrin sulfur quantum dots and curcumin sensing system can be used for Fe in actual samples. 3+ Analytical testing.
[0039] Table 1
[0040] Table 2
[0041] Example 6
[0042] In order to explore the selectivity and interference of β-cyclodextrin sulfur quantum dots in detecting curcumin, a variety of ions (K + , Ca 2+ 、Na + Mg 2+ 、Al 3+ 、Zn 2+ , Fe 3+), some common molecules (aspartic acid, cysteine, histidine, phenylalanine, serine, urea, ascorbic acid) and common pigments (β-carotene, chlorophyll, lemon yellow, sunset yellow) were evaluated as interfering species. The results showed that most interfering species had little effect on the detection of curcumin, and only Cur caused a significant change in the fluorescence intensity of β-cyclodextrin sulfur quantum dots. While detecting Cur, the above-mentioned interfering substances were introduced into the detection system to verify the anti-interference ability of β-cyclodextrin sulfur quantum dots in detecting curcumin. Figure 8 As shown, (the concentrations of curcumin and other interfering substances are 20 μmol / L and 1.0 μmol / L, respectively. The purple bar represents the fluorescence response of the sensing system to a specific interfering species. The pink bar shows the fluorescence response of the sensing system in the presence of 20 μmol / L curcumin and 1.0 μmol / L corresponding interfering substances) When interfering substances coexist with Cur, most of the interfering substances have little effect on the fluorescence intensity of the detection system. The above data can show that β-cyclodextrin sulfur quantum dots have good selectivity and anti-interference ability in detecting curcumin.
[0043] The contents not described in detail in the specification of the present invention belong to the prior art known to the professional and technical personnel in the field. Although the illustrative specific embodiments of the present invention are described above to facilitate the understanding of the present invention by the technical personnel in the field, it should be clear that the present invention is not limited to the scope of the specific embodiments. For the ordinary technical personnel in the field, as long as various changes are within the spirit and scope of the present invention defined and determined by the attached claims, these changes are obvious, and all inventions and creations using the concept of the present invention are protected.
Claims
1. A method for simultaneous detection of curcumin and Fe 3+ The β-cyclodextrin sulfur quantum dots are characterized by: The β-cyclodextrin sulfur quantum dots are spherical in structure, and the particle size distribution is between 0.55 nm and 1.25 nm.
2. A method for simultaneously detecting curcumin and Fe according to claim 1 3+ The β-cyclodextrin sulfur quantum dots are characterized by: The lattice spacing of the β-cyclodextrin sulfur quantum dots is 0.214 nm, and the average particle size is 0.9±0.1 nm.
3. A method for simultaneously detecting curcumin and Fe according to claim 1 3+ The β-cyclodextrin sulfur quantum dots are characterized by: The optimal excitation of the β-cyclodextrin sulfur quantum dots is at 320 nm, and the maximum emission peak is at 420 nm.
4. A method for simultaneously detecting curcumin and Fe according to claim 1 3+ The β-cyclodextrin sulfur quantum dots are characterized by: The linear range of the β-cyclodextrin sulfur quantum dots for detecting curcumin is 0.50-90 μM, and the detection sensitivity is 23 nM.
5. A method for simultaneously detecting curcumin and Fe according to claim 1 3+ The β-cyclodextrin sulfur quantum dots are characterized by: The β-cyclodextrin sulfur quantum dots detect Fe in the curcumin system 3+ The linear range of the assay was 0.80-100 μM, and the detection sensitivity was 0.58 μM.
6. A method for simultaneously detecting curcumin and Fe according to claim 1 3+ The method for preparing β-cyclodextrin sulfur quantum dots is characterized by: Sodium hydroxide, sublimated sulfur powder and β-cyclodextrin are added into ultrapure water, heated and stirred until completely dissolved, and then the mixed solution is transferred to a polytetrafluoroethylene reactor for high temperature and high pressure reaction, and the β-cyclodextrin sulfur quantum dots are obtained after purification by dialysis and freeze drying.
7. A method for simultaneously detecting curcumin and Fe according to claim 6. 3+ The method for preparing β-cyclodextrin sulfur quantum dots is characterized by: The mass ratio of the sublimated sulfur powder to β-cyclodextrin is (1-1.5):(1-1.3).
8. A method for simultaneously detecting curcumin and Fe according to claim 6 3+ The method for preparing β-cyclodextrin sulfur quantum dots is characterized by: The temperature of the heating and stirring is 50°C and the time is 30 min; the specific steps of the dialysis purification are: dialysis in a dialysis bag with a molecular weight cutoff of 3500 Da for 12 to 16 hours; the time of the freeze-drying is: 24 hours; the temperature of the high temperature and high pressure reaction is 170°C and the time is 6 hours.
9. A β-cyclodextrin sulfur quantum dot prepared by the preparation method according to any one of claims 6 to 8 in the presence of curcumin and Fe 3 + Applications in fluorescence sensing.
10. The use according to claim 9, characterized in that: Used for the detection of curcumin in beverages.