CN111876149A - Preparation method and application of ratio type fluorescent carbon dots for detecting sertraline and glutathione - Google Patents
Preparation method and application of ratio type fluorescent carbon dots for detecting sertraline and glutathione Download PDFInfo
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- CN111876149A CN111876149A CN202010734688.1A CN202010734688A CN111876149A CN 111876149 A CN111876149 A CN 111876149A CN 202010734688 A CN202010734688 A CN 202010734688A CN 111876149 A CN111876149 A CN 111876149A
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
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Abstract
A preparation method and application of ratio-type fluorescent carbon dots for detecting sertraline and glutathione belong to the field of fluorescent carbon dots, and the purpose is to provide a preparation method and application of ratio-type fluorescent carbon dots with specific recognition effect on sertraline and glutathione. Dissolving neutral red and polyethyleneimine in secondary water, performing ultrasonic treatment to obtain a uniformly mixed solution, transferring the uniformly mixed solution to a hydrothermal reaction kettle, reacting for 4-8h at the temperature of 150-200 ℃, standing and cooling to room temperature after the reaction is stopped, centrifuging to remove insoluble substances, taking supernatant, performing dialysis treatment in a glass container for at least three days through a dialysis bag of 500-1000Da to obtain a pure carbon point aqueous solution, and performing freeze drying to obtain the carbon point emitted by orange-red fluorescence. The prepared ratio-type fluorescent carbon dots have a specific recognition effect on sertraline and glutathione, and carbon dot fluorescence presents orange-green-orange reversible transformation, so that the ratio-type fluorescent carbon dots are used for detecting sertraline and glutathione, and are good in selectivity and high in sensitivity.
Description
Technical Field
The invention belongs to the technical field of fluorescent carbon dots, and particularly relates to a preparation method and application of a ratio type fluorescent carbon dot for detecting sertraline and glutathione.
Background
Sertraline is a potent and selective neuronal 5-hydroxytryptamine reuptake inhibitor, and at clinical doses, sertraline blocks platelet uptake of 5-hydroxytryptamine in humans, with only a weak effect on norepinephrine and dopamine. In vitro studies have shown that sertraline has no significant affinity for adrenergic receptors, cholinergic receptors, GABA receptors, dopaminergic receptors, histamine receptors, 5-hydroxytryptamine receptors (or benzodiazepine receptors, antagonism of these receptors is believed to be associated with sedative, anticholinergic and cardiotoxicity effects of other psychotropic drugs, sertraline has no inhibitory effect on monoamine oxidase, sertraline has a plasma protein binding rate of 98%, and is metabolized primarily by the liver, sertraline overdose symptoms include adverse reactions due to 5-hydroxytryptamine, such as lethargy, gastrointestinal discomfort, tachycardia, tremor, agitation and dizziness, etc., sertraline has no specific antidote, and thus, rapid and sensitive detection of sertraline is of great importance in medical diagnosis. It plays a key role in guiding many physiological and pathological processes in mammalian systems. Abnormal levels of GSH in humans can affect many cellular functions, including the maintenance of intracellular redox activity, signaling, gene regulation, and liver damage, and are closely related to cancer, alzheimer's disease, and various types of cardiovascular diseases. Therefore, the fluorescent material capable of rapidly and sensitively detecting sertraline and glutathione has potential application value in organisms.
The carbon dots have good application prospect in various fields such as biological imaging, environmental monitoring, nano materials and the like due to the characteristics of excellent luminescence property, good chemical stability, biocompatibility, surface function adjustability and the like. Most of the carbon dots synthesized at present emit blue-green fluorescence, which limits the application of the carbon dots in biomedicine and photoelectric devices. A few documents report the application of long-wave emission of carbon spots, but the long-wave fluorescent carbon spots only have a single emission peak and the intensity change of the single emission peak, and are easily influenced by other concentrations and external environmental conditions. The ratiometric fluorescence method measures the fluorescence intensity at two different wavelengths, and uses the ratio as a signal parameter to determine the target. It can provide internal correction environment interference and eliminate fluctuation of excitation light intensity, provide quantitative analysis accuracy, break through the defects that a probe giving single fluorescence intensity is easily influenced by a detection substrate, photobleaching and the like, and has received great attention in recent years. Therefore, designing and synthesizing the long-wave emission ratio type fluorescent carbon dots to construct a biosensing platform of sertraline and glutathione has extremely important research significance.
Disclosure of Invention
The invention aims to provide a ratio type fluorescent carbon dot which can be simply synthesized and has specific recognition effect on sertraline and glutathione, and a preparation method and application thereof.
The invention adopts the following technical scheme:
a preparation method of ratio type fluorescent carbon dots for detecting sertraline and glutathione comprises the following steps:
firstly, dissolving neutral red and polyethyleneimine in secondary water according to a proportion, and performing ultrasonic treatment to obtain a uniformly mixed solution;
secondly, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 4-8h at the temperature of 150-;
and step three, freeze-drying the carbon dot aqueous solution to obtain the carbon dots with orange-red fluorescence emission.
In the first step, the mass ratio of the neutral red to the polyethyleneimine to the secondary water is 1-4:5-50: 10000.
A ratiometric fluorescent carbon dot is applied to detection of sertraline and glutathione.
A ratio type fluorescent carbon dot is applied to constructing a visual fluorescent sensor.
The invention has the following beneficial effects:
compared with the prior art, the invention has the following beneficial effects:
1. the method has simple operation steps, and the ratio type long-wavelength emission fluorescent carbon dots can be obtained without surface passivating agent treatment or modification.
2. The carbon dots prepared by the method have good solubility and dispersibility in an aqueous solution.
3. The quantum yield of the carbon dots prepared by the method is high, rhodamine B (the quantum yield in ethanol is 89%) is used as a reference substance, and the quantum yield of the obtained carbon dots is generally between 7.6% and 12.9%.
4. The prepared ratio-type fluorescent carbon dots have a specific recognition effect on sertraline and glutathione, and the carbon dot fluorescence presents green-orange reversible transformation, so that the ratio-type fluorescent carbon dots are used for detecting sertraline and/or glutathione, and are good in selectivity and high in sensitivity.
Drawings
FIG. 1 is an infrared spectrum of a ratiometric fluorescent carbon dot prepared in example 1 of the present invention, wherein the abscissa is the detection wavelength and the ordinate is the transmittance.
FIG. 2 is an XPS spectrum of ratiometric fluorescent carbon dots prepared in example 1 of the present invention.
FIG. 3 shows the UV absorption spectrum and fluorescence excitation-emission spectrum of a ratiometric fluorescent carbon dot prepared in example 1 of the present invention.
FIG. 4 is a spectrum diagram of a fluorescence emission curve of a ratiometric fluorescent carbon dot prepared in example 1 as a function of excitation wavelength.
FIG. 5 is a graph showing the change in fluorescence of carbon spots in the presence of different concentrations of sertraline and I530/I593Working curve under the ratio.
FIG. 6 is a graph showing the change in fluorescence of CDs @ sertraline in the presence of different concentrations of glutathione and I530/I593Working curve under the ratio.
FIG. 7 is an image of a ratio-type fluorescent carbon dot prepared in example 1 of the present invention, which is a PC-12 cell.
Detailed Description
Example 1
A preparation method of ratio type fluorescent carbon dots for detecting sertraline and glutathione comprises the following steps:
1) weighing neutral red and polyethyleneimine, dissolving in secondary water, and performing ultrasonic treatment to obtain a uniformly mixed solution; the mass ratio of the neutral red to the polyethyleneimine to the secondary water is 2.5:20: 10000;
2) transferring the mixed solution into a hydrothermal reaction kettle, reacting at 180 ℃ for 6 h, standing and cooling to room temperature after the reaction is stopped, centrifuging to remove insoluble substances, taking supernatant, and dialyzing in a glass container for at least three days through a 500-plus-1000 Da dialysis bag to obtain a pure carbon dot aqueous solution;
3) and (3) freeze-drying the carbon dot aqueous solution to obtain the carbon dots with orange-red fluorescence emission. The relative quantum yield of rhodamine B as a reference substance is 12.9 percent.
Example 2
A preparation method of ratio type fluorescent carbon dots for detecting sertraline and glutathione comprises the following steps:
1) weighing neutral red and polyethyleneimine, dissolving in secondary water, and performing ultrasonic treatment to obtain a uniformly mixed solution; the mass ratio of the neutral red to the polyethyleneimine to the secondary water is 2.5:10: 10000;
2) transferring the mixed solution into a hydrothermal reaction kettle, reacting at 180 ℃ for 6 h, standing and cooling to room temperature after the reaction is stopped, centrifuging to remove insoluble substances, taking supernatant, and dialyzing in a glass container for at least three days through a 500-plus-1000 Da dialysis bag to obtain a pure carbon dot aqueous solution;
3) and (3) freeze-drying the carbon dot aqueous solution to obtain the carbon dots with orange-red fluorescence emission. Relative quantum yield of rhodamine B as a reference substance is 8.3%.
Example 3
A preparation method of ratio type fluorescent carbon dots for detecting sertraline and glutathione comprises the following steps:
1) weighing neutral red and polyethyleneimine, dissolving in secondary water, and performing ultrasonic treatment to obtain a uniformly mixed solution; the mass ratio of the neutral red to the polyethyleneimine to the secondary water is 2.5:30: 10000;
2) transferring the mixed solution into a hydrothermal reaction kettle, reacting at 180 ℃ for 6 h, standing and cooling to room temperature after the reaction is stopped, centrifuging to remove insoluble substances, taking supernatant, and dialyzing in a glass container for at least three days through a 500-plus-1000 Da dialysis bag to obtain a pure carbon dot aqueous solution;
3) and (3) freeze-drying the carbon dot aqueous solution to obtain the carbon dots with orange-red fluorescence emission. Relative quantum yield of rhodamine B as a reference substance is 9.4%.
The characterization of the orange fluorescent carbon dot prepared in the example 1 of the invention is shown in figures 1 and 2. The infrared spectrogram proves that the amino-containing compound has a benzene ring structure and contains amino on the surface. The XPS spectrum shows that the carbon dots have C-N, C ═ and C-OH, and C ═ O structures, and further shows that the surface of the carbon dots contains amino groups.
The optical property spectrograms of the ratiometric fluorescent carbon dots prepared in example 2 of the invention are shown in fig. 3 and 4. The UV-Vis absorption line of the carbon point has three absorption peaks at 275nm, 369nm and 450 nm. The fluorescent material shows an emission wavelength of 593nm under the excitation of 480nm and shows orange red fluorescence. Fig. 4 is a spectrum of emission spectra of the carbon dots at different excitation wavelengths, showing that the carbon dots have excitation wavelength dependence.
FIG. 5 shows the sensitivity of ratiometric fluorescent carbon dots prepared in example 1 of the present invention to sertraline, wherein the linear range is 5-45 μ M, the detection limit is 2.78 μ M, and the fluorescence of the carbon dots changes from orange to green.
The fluorescence recovery diagram of carbon dot @ sertraline in the presence of glutathione in the embodiment 6 of the invention is shown in FIG. 6, the linear range of the fluorescence recovery diagram is 0.1-1.1 mM, the detection limit is 84.6 mu M, and the fluorescence of the carbon dot is changed from green to orange.
An image of a cell of the ratiometric fluorescent carbon dot prepared in example 1 of the present invention is shown in FIG. 7. The murine pheochromocytoma cell PC-12 is incubated in an orange fluorescent carbon dot aqueous solution (pH 7.4) for 2 hours, the carbon dots are fully dispersed to a cytoplasmic region, weak green fluorescence is presented in a green channel, bright orange fluorescence is presented in an orange channel, after sertraline is added, the green fluorescence is gradually enhanced, the orange fluorescence is unchanged, and then after glutathione is added, the fluorescence is gradually restored to the original state. The green channel and the orange channel are compared, and the change of the fluorescence intensity of adding sertraline and glutathione into the two channels can be obviously observed, which indicates that the orange fluorescent carbon dot can be used for constructing a ratio sensing platform of sertraline and glutathione in an organism.
Claims (4)
1. A preparation method of ratio type fluorescent carbon dots for detecting sertraline and glutathione is characterized by comprising the following steps: the method comprises the following steps:
firstly, dissolving neutral red and polyethyleneimine in secondary water according to a proportion, and performing ultrasonic treatment to obtain a uniformly mixed solution;
secondly, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 4-8h at the temperature of 150-;
and step three, freeze-drying the carbon dot aqueous solution to obtain the carbon dots with orange-red fluorescence emission.
2. The method for preparing a ratiometric fluorescent carbon dot for detecting sertraline and glutathione according to claim 1, wherein the ratio of the fluorescent carbon dot to the sertraline is as follows: in the first step, the mass ratio of the neutral red to the polyethyleneimine to the secondary water is 1-4:5-50: 10000.
3. A ratiometric fluorescent carbon dot prepared by the preparation method of claim 1 is applied to detection of sertraline and glutathione.
4. The ratio-type fluorescent carbon dot prepared by the preparation method of claim 1 is applied to the construction of a visual fluorescent sensor.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113278415A (en) * | 2021-04-07 | 2021-08-20 | 长春工业大学 | Preparation method and application of sulfur-nitrogen co-doped yellow fluorescent carbon dots |
| CN113480731A (en) * | 2021-07-22 | 2021-10-08 | 西安工业大学 | Detectable Cu2+And ClO-Preparation method of fluorescent carbon dot and hydrogel |
| CN113800501A (en) * | 2021-10-08 | 2021-12-17 | 山西大学 | Preparation method and application of orange-red fluorescent carbon dots for detecting pH and arginine |
| CN114854403A (en) * | 2022-04-21 | 2022-08-05 | 山西大学 | Orange fluorescent carbon dot and preparation method and application thereof |
| CN114956049A (en) * | 2022-06-17 | 2022-08-30 | 山西大学 | Long wavelength ratio fluorescent carbon dot and preparation method and application thereof |
| CN115029131A (en) * | 2022-05-27 | 2022-09-09 | 福建医科大学 | Noradrenaline modified carbon dot and preparation method and application thereof |
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| CN109486481A (en) * | 2018-11-21 | 2019-03-19 | 山西大学 | One kind is for detecting Ag+With the Ratio-type fluorescent carbon point of GSH and preparation method thereof |
| WO2020112792A1 (en) * | 2018-11-28 | 2020-06-04 | CARPENTER, Alexis, Wells | Systems, compositions, and/or methods utilizing carbon dots |
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- 2020-07-28 CN CN202010734688.1A patent/CN111876149B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109486481A (en) * | 2018-11-21 | 2019-03-19 | 山西大学 | One kind is for detecting Ag+With the Ratio-type fluorescent carbon point of GSH and preparation method thereof |
| WO2020112792A1 (en) * | 2018-11-28 | 2020-06-04 | CARPENTER, Alexis, Wells | Systems, compositions, and/or methods utilizing carbon dots |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113278415A (en) * | 2021-04-07 | 2021-08-20 | 长春工业大学 | Preparation method and application of sulfur-nitrogen co-doped yellow fluorescent carbon dots |
| CN113480731A (en) * | 2021-07-22 | 2021-10-08 | 西安工业大学 | Detectable Cu2+And ClO-Preparation method of fluorescent carbon dot and hydrogel |
| CN113800501A (en) * | 2021-10-08 | 2021-12-17 | 山西大学 | Preparation method and application of orange-red fluorescent carbon dots for detecting pH and arginine |
| CN114854403A (en) * | 2022-04-21 | 2022-08-05 | 山西大学 | Orange fluorescent carbon dot and preparation method and application thereof |
| CN115029131A (en) * | 2022-05-27 | 2022-09-09 | 福建医科大学 | Noradrenaline modified carbon dot and preparation method and application thereof |
| CN114956049A (en) * | 2022-06-17 | 2022-08-30 | 山西大学 | Long wavelength ratio fluorescent carbon dot and preparation method and application thereof |
| CN114956049B (en) * | 2022-06-17 | 2023-07-18 | 山西大学 | Long wavelength ratio fluorescent carbon dot and preparation method and application thereof |
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