CN115029132A - Preparation method of novel dopamine functionalized fluorescent carbon dots, product and application thereof - Google Patents
Preparation method of novel dopamine functionalized fluorescent carbon dots, product and application thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a novel dopamine functional fluorescent carbon dot, a product and application thereof, and belongs to the technical field of preparation of functional fluorescent carbon dots. The preparation method is simple and easy to operate, and can realize the preparation of the industrial dopamine functional fluorescent carbon dots, and the obtained product has double emission peaks at the wavelengths of 420nm and 460 nm. Because the dopamine functional fluorescent carbon dots contain phosphate bonds, the fluorescence intensity at the wavelength of 460nm is reduced and the fluorescence intensity at the wavelength of 420nm is not influenced after the dopamine functional fluorescent carbon dots are oxidized by hypochlorite; meanwhile, as the concentration of hypochlorite is increased, the fluorescence intensity ratio of the dopamine functional fluorescent carbon dots at the 420nm and 460nm wavelength is reduced, so that a fluorescence ratio method for detecting the dopamine functional fluorescent carbon dots can be established, and the method has the advantages of high sensitivity, good accuracy and good selectivity.
Description
Technical Field
The invention belongs to the technical field of preparation of dopamine functional fluorescent carbon dots, and relates to a preparation method of a novel dopamine functional fluorescent carbon dot, and a product and application thereof.
Background
Hypochlorite (ClO) - ) Is a strong oxidant and is widely applied to production processes of disinfection, deodorization and the like in water treatment. Due to ClO - The concentration is too low to effectively kill pathogenic bacteria, so the control of hypochlorite (ClO) in water must be strict - ) The concentration of (c); in the internal immune system of the body, ClO - Also plays an important role in resisting pathogenic microorganisms, pathogens and viruses. Once the concentration in biological cells exceeds the normal range, the biological macromolecules such as phospholipid, protein, DNA and the like can be seriously damaged, and a series of pathological changes such as arteriosclerosis, arthritis, rheumatoid arthritis, lung inflammation, neuron degeneration, cancer and the like are caused in vivo. Therefore, drinking water and hypochlorite (ClO) in vivo are required - ) The concentration is monitored and controlled. Currently, hypochlorite (ClO) - ) The detection method of (3) includes a colorimetric method, a fluorescent method, a chemiluminescence method, an electrochemical method and the like. The fluorescence method has the advantages of high sensitivity and quick response, and is reported by a great number of researchers, wherein the fluorescent nano material is widely applied to fluorescence analysis due to high luminous efficiency, and particularly, fluorescent carbon dots are paid more and more attention by the researchers due to simple synthesis method and low toxicity.
A ratiometric fluorescent probe is a fluorescent material having two emission wavelengths, the ratio of the intensities of which is linear with the concentration of the target analyte. The ratiometric fluorescent probe has the functions of self-regulation and internal standard establishment, and can reduce the interference of other factors. Therefore, compared with the common fluorescent probe, the ratiometric fluorescent probe has stronger anti-interference capability, higher sensitivity and selectivity, and has larger application potential in practical analysis. Therefore, an increasing number of researchers are interested in the study of the fluorescence ratio method: for example, Huang and his collaborators designed a formulation based on a ketone of valolol anddetection of ClO by near-infrared ratiometric fluorescent probe of coumarin - The probe has a red emission peak at 685nm, when ClO is added - When the fluorescence intensity at 486nm is increased, the fluorescence intensity at 685nm is decreased, and the ratio of the two fluorescence intensities can be changed along with the ClO - Changes in concentration, and thus can be used for fluorescence ratiometric detection of ClO - (ii) a Sun and his collaborators reported a ClO based on Metal Organic Frameworks (MOFs) - A ratiometric fluorescence detection method, wherein the fluorescent MOFs has dual fluorescence emission signals, ClO, at 433nm and 621nm - Can reduce the blue fluorescence at 433nm, keep the fluorescence at 621nm stable, and the fluorescence intensity ratio of the two positions can follow the ClO - Changes in concentration, and thus can be used for fluorescence ratiometric detection of ClO - 。
The fluorescence ratio method is limited by the complicated reaction and the inconvenient operation of synthesizing the ratio fluorescent probe. Therefore, it is of great significance to explore a method for simply and rapidly preparing ratiometric fluorescent probes.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing a novel dopamine-functionalized fluorescent carbon dot; the second purpose of the invention is to provide a novel dopamine functionalized fluorescent carbon dot; the invention also aims to provide a novel dopamine functionalized fluorescent carbon dot for preparing and detecting hypochlorite (ClO) - ) The ratiometric fluorescent probes of (1).
In order to achieve the purpose, the invention provides the following technical scheme:
1. a preparation method of a novel dopamine functionalized fluorescent carbon dot comprises the following steps:
mixing the fluorescent carbon dots (C-dots) and dopamine in water, adding a buffer solution to adjust the pH value to 8.0, and reacting at 20-35 ℃ for 3-10min to obtain the dopamine functionalized fluorescent carbon dots (DA-dots).
Preferably, the volume ratio of the fluorescent carbon dots (C-dots), the dopamine aqueous solution and the water is 200:120-180: 400-500;
the concentration of the dopamine aqueous solution is 1 mM.
Further preferably, the fluorescent carbon dots (C-dots) are prepared as follows:
(1) dissolving 3-hydroxyphenylboronic acid in water, adjusting the pH to 9.0, and stirring to fully dissolve the 3-hydroxyphenylboronic acid;
(2) filling nitrogen (N) into the solution dissolved in the step (1) 2 ) Removing oxygen in the solution, filling the solution into a reaction kettle, and reacting for 6-10h at the temperature of 150-;
(3) and cooling to room temperature after the reaction is finished, centrifuging and taking supernate to obtain the fluorescent carbon dots (C-dots).
Preferably, the mass-volume ratio of the 3-hydroxyphenylboronic acid to the water is 0.2:20, g: mL.
Preferably, a 0.1M NaOH solution is used in the pH adjustment.
Preferably, the centrifugation is performed at 10000rpm for 10 min.
Preferably, the buffer solution is a phosphate buffer solution with a concentration of 40 mM.
2. The dopamine functionalized fluorescent carbon dots (DA-dots) prepared according to the preparation method are provided.
3. The dopamine functionalized fluorescent carbon dots (DA-dots) are used for preparing and detecting hypochlorite (ClO) - ) The ratiometric fluorescent probes of (1).
The invention has the beneficial effects that:
1. the invention discloses a novel preparation method of dopamine functional fluorescent carbon dots, which is mainly used for reacting fluorescent carbon dots (C-dots) with dopamine to obtain the dopamine functional fluorescent carbon dots (DA-dots).
2. The invention also discloses a novel dopamine functional fluorescent carbon dot (DA-dots) which has double emission peaks at the wavelengths of 420nm and 460 nm. The dopamine-functionalized fluorescent carbon dots (DA-dots) of the present invention contain a phosphate ester bond and are substituted with hypochlorite (ClO) - ) After oxidation, the fluorescence intensity at 460nm wavelength is reduced, while the fluorescence intensity at 420nm wavelength is not affected; simultaneously with hypochlorite (ClO) - ) Increase in concentrationThe fluorescence intensity ratio of the dopamine functional fluorescent carbon dots (DA-dots) at the 420nm and 460nm wavelengths is reduced, so that a fluorescence ratio method for detecting the dopamine functional fluorescent carbon dots (DA-dots) can be established, and the method has the advantages of high sensitivity, good accuracy and good selectivity.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims thereof.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1A is a graph of fluorescence emission spectra of boronocarbon acid spots containing different groups (wherein a is a 3-hydroxyphenylboronic acid carbon spot, B is a 3-aminophenylboronic acid carbon spot, C is a 4-formylphenylboronic acid, d is a 4-mercaptophenylboronic acid carbon spot, and e is a 4-formylphenylboronic acid carbon spot), B is a fluorescence emission spectrum of the fluorescent carbon spot (C-dots) and the dopamine-functionalized fluorescent carbon spot (DA-dots) prepared in example 1, and C is a graph of the fluorescent carbon spot (C-dots) and the dopamine-functionalized fluorescent carbon spot (DA-dots) prepared in example 1 under natural light and fluorescence irradiation;
FIG. 2 shows dopamine-functionalized fluorescent carbon dots (DA-dots) prepared in example 1 as a detection Probe (Probe) to which hypochlorite (ClO) is added - ) The change in fluorescence intensity before and after;
FIG. 3 is a graph showing fluorescence emission spectra of the dopamine functionalized fluorescent carbon dots (DA-dots) prepared in example 1 under excitation of different wavelengths (255nm, 265nm, 275nm, 285nm and 295nm), and a graph showing scanning electron microscopy of the dopamine functionalized fluorescent carbon dots (DA-dots) prepared in example 1;
FIG. 4 shows dopamine functionalized fluorescent carbon dots (DA-dots) (a) prepared in example 1 and hypochlorite (ClO) added thereto at different pH values under excitation of 460nm - ) Fluorescence emission spectrum of the rear (b)Strength;
FIG. 5 shows the dopamine functionalized fluorescent carbon dots (DA-dots) (a) prepared in example 1 and hypochlorite (ClO) added thereto at different temperatures under excitation of 460nm - ) Fluorescence emission spectrum intensity of the latter (b);
FIG. 6 shows the addition of hypochlorite (ClO) to the fluorescence Probe (Probe) of the dopamine-functionalized fluorescent carbon dots (DA-dots) prepared in example 1 under the excitation of 460nm - ) The intensity of fluorescence emission spectra after post-reaction for different times;
FIG. 7A is a graph showing the addition of hypochlorite (ClO) at various concentrations to the fluorescence Probe (Probe) for dopamine-functionalized fluorescent carbon dots (DA-dots) prepared in example 1 - ) The change of the after-fluorescence emission spectrum, B is the ratio of the fluorescence intensities (I) 460nm /I 420nm ) With hypochlorite (ClO) added correspondingly - ) A linear fit curve of concentration;
FIG. 8 is a graph showing the addition of different substances to the fluorescence intensity ratio (I) to the fluorescence Probe (Probe) of the dopamine functionalized fluorescent carbon dots (DA-dots) prepared in example 1 460nm /I 420nm ) The influence of (c).
Detailed Description
The following embodiments of the present invention are provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and examples may be combined with each other without conflict.
The solvent in the solution used in the following examples was water, the names, types and manufacturers of the used laboratory instruments are shown in table 1, and the names, specifications (purity) and manufacturers of the laboratory reagents are shown in table 2.
TABLE 1 name, model and manufacturer of the laboratory instruments
TABLE 2 name, Specification (purity) and manufacturer of the test reagents
Example 1
The preparation method of the novel dopamine functionalized fluorescent carbon dots (DA-dots) specifically comprises the following steps:
(1) preparation of fluorescent carbon dots (C-dots): firstly, dissolving 3-hydroxyphenylboronic acid in water according to the mass-volume ratio of 0.2:20 g: mL, adjusting the pH to 9.0 by adopting a 0.1M NaOH solution, and stirring to fully dissolve the solution; then, nitrogen gas (N) was introduced thereinto 2 ) Removing oxygen in the solution, filling the solution into a reaction kettle, and reacting for 8 hours at 160 ℃; after the reaction is finished, cooling to room temperature, centrifuging at 10000rpm for 10min, taking supernatant, and placing to obtain the fluorescent carbon dots (C-dots).
(2) Preparing dopamine functionalized fluorescent carbon dots (DA-dots): mixing the fluorescent carbon dots (C-dots) and dopamine in water according to a volume ratio of 200:150:500, adding a phosphate buffer solution with the concentration of 40mM to adjust the pH value to 8.0, and reacting for 5min at 25 ℃ to obtain the dopamine functionalized fluorescent carbon dots (DA-dots).
Example 2
The preparation method of the novel dopamine functionalized fluorescent carbon dots (DA-dots) specifically comprises the following steps:
(1) preparation of fluorescent carbon dots (C-dots): firstly, dissolving 3-hydroxyphenylboronic acid in water according to the mass-volume ratio of 0.2:20 g: mL, adjusting the pH to 9.0 by adopting a 0.1M NaOH solution, and stirring to fully dissolve the solution; then, nitrogen gas (N) was introduced thereinto 2 ) Removing oxygen in the solution, filling the solution into a reaction kettle, and reacting for 6 hours at 180 ℃; after the reaction is finished, cooling to room temperature, centrifuging at 10000rpm for 10min, taking supernatant, and placing to obtain the fluorescent carbon dots (C-dots).
(2) Preparing dopamine functional fluorescent carbon dots (DA-dots): mixing the fluorescent carbon dots (C-dots), dopamine with the concentration of 1mM and water according to the volume ratio of 200:180:400, adding phosphate buffer solution with the concentration of 40mM to adjust the pH value to 8.0, and reacting for 3min at 35 ℃ to obtain the dopamine functionalized fluorescent carbon dots (DA-dots).
Example 3
The preparation method of the novel dopamine functionalized fluorescent carbon dots (DA-dots) specifically comprises the following steps:
(1) preparation of fluorescent carbon dots (C-dots): firstly, dissolving 3-hydroxyphenylboronic acid in water according to the mass-volume ratio of 0.2:20 g: mL, adjusting the pH to 9.0 by adopting a 0.1M NaOH solution, and stirring to fully dissolve the solution; then, nitrogen gas (N) was introduced thereinto 2 ) Removing oxygen in the solution, putting the solution into a reaction kettle, and reacting for 10 hours at 150 ℃; after the reaction is finished, cooling to room temperature, centrifuging at 10000rpm for 10min, taking supernatant, and placing to obtain the fluorescent carbon dots (C-dots).
(2) Preparing dopamine functional fluorescent carbon dots (DA-dots): mixing the fluorescent carbon dots (C-dots), the dopamine aqueous solution with the concentration of 1mM and water according to the volume ratio of 200:120:500, adding the phosphate buffer solution with the concentration of 40mM to adjust the pH value to 8.0, and reacting for 10min at 20 ℃ to obtain the dopamine functionalized fluorescent carbon dots (DA-dots).
Performance testing
In FIG. 1, A is a fluorescence emission spectrum of different boronocarbon sites containing different groups (where a is a carbon site of 3-hydroxyphenylboronic acid, B is a carbon site of 3-aminophenylboronic acid, C is a carbon site of 4-formylphenylboronic acid, d is a carbon site of 4-mercaptophenylboronic acid, and e is a carbon site of 4-formylphenylboronic acid), B is a fluorescence emission spectrum of the fluorescent carbon sites (C-dots) and the dopamine functionalized fluorescent carbon sites (DA-dots) prepared in example 1, and C is a picture of the fluorescent carbon sites (C-dots) and the dopamine functionalized fluorescent carbon sites (DA-dots) prepared in example 1 under natural light and fluorescence irradiation. Fluorescence emission spectra of 0.2g mass of the carbon dots of 3-hydroxyphenylboronic acid, 3-aminophenylboronic acid, 4-mercaptophenylboronic acid and 4-formylphenylboronic acid when excited at 25 ℃ and 300nm are shown as A in FIG. 1, and the fluorescence intensity of 3-hydroxyphenylboronic acid is the largest among the carbon dots of 3-hydroxyphenylboronic acid, 3-aminophenylboronic acid, 4-mercaptophenylboronic acid and 4-formylphenylboronic acid, so that the fluorescent carbon dots (C-dots) can be prepared by subsequently selecting 3-hydroxyphenylboronic acid as a raw material. Fluorescence emission spectrograms of the dopamine-functionalized fluorescent carbon dots (DA-dots) and the fluorescent carbon dots (C-dots) excited at 25 ℃ and 285nm and having the concentration of 10 mu L are shown as B in figure 1, and compared with the fluorescent carbon dots (C-dots) having an emission peak only at the wavelength of 420nm, the dopamine-functionalized fluorescent carbon dots (DA-dots) serving as detection probes (probes) have emission peaks at the wavelengths of 420nm and 460nm and belong to double emission peaks. A picture of the fluorescent carbon dots (C-dots) and the dopamine functionalized fluorescent carbon dots (DA-dots) prepared in example 1 under natural light and fluorescent irradiation is shown as C in FIG. 1.
FIG. 2 shows dopamine-functionalized fluorescent carbon dots (DA-dots) prepared in example 1 as a detection Probe (Probe) to which hypochlorite (ClO) is added - ) The fluorescence intensity before and after the change. Adding 50M hypochlorite (ClO) to dopamine-functionalized fluorescent carbon dots (DA-dots) - ) Then, the fluorescence peak intensity at 460nm was reduced by 56%, and the fluorescence peak intensity at 420nm was hardly affected. Therefore, the signal intensity at 420nm can be used as a reference to improve the detection sensitivity and selectivity.
In FIG. 3, A is the fluorescence emission spectrum of the dopamine functionalized fluorescent carbon dots (DA-dots) prepared in example 1 under different wavelength excitation (255nm, 265nm, 275nm, 285nm and 295nm), and B is the scanning electron micrograph of the dopamine functionalized fluorescent carbon dots (DA-dots) prepared in example 1. As can be seen from A in FIG. 3, the dopamine functionalized fluorescent carbon dots (DA-dots) prepared in example 1 at a concentration of 10. mu.L had an optimum excitation wavelength for the dopamine functionalized fluorescent carbon dots (DA-dots) prepared in example 1, because the peak intensity in the fluorescence emission spectrum increased sequentially when the excitation wavelength was changed from 255nm, 265nm, 275nm, and 285nm, and the peak intensity in the fluorescence emission spectrum decreased when the excitation wavelength was changed from 285nm to 295 nm. As can be seen from B in FIG. 3, the particle size of the dopamine functionalized fluorescent carbon dots (DA-dots) prepared in example 1 is about 1 to 2 nm.
The dopamine prepared in example 1 was functionalizedDetection of hypochlorite (ClO) by using photo-carbon dots (DA-dots) as ratiometric fluorescent probe - ) The influence of various conditions in the detection process on the detection effect is as follows:
(1) influence of solution pH value in detection process
FIG. 4 shows dopamine functionalized fluorescent carbon dots (DA-dots) (a) prepared in example 1 and hypochlorite (ClO) added thereto at different pH values under excitation of 460nm - ) Fluorescence emission spectrum intensity of the latter (b). The dopamine-functionalized fluorescent carbon dots (DA-dots) prepared in example 1 were prepared in 5 parts by weight to give a 10. mu.L solution, the pH of the solution was adjusted to 4.4, 6.0, 7.4, 8.0 and 9.0 using a phosphate buffer solution, and 50. mu.M hypochlorite (ClO) was added to the solution - ) And after 5min of reaction, fluorescence emission spectrum detection is carried out under the excitation of wavelength of 285nm at 25 ℃. Hypochlorite (ClO) was added as the pH increased from 4.4 to 9.0 - ) The fluorescence intensity at 420nm before and after the reaction was hardly affected. Hypochlorite (ClO) was added to the solution at a pH of 4.4 and 7.4 - ) Fluorescence intensity at 460nm before and after reaction is unchanged, fluorescence intensity of dopamine-functionalized fluorescent carbon dots (DA-dots) is obviously increased when pH value is 8.0 and 9.0, and hypochlorite (ClO) is added - ) The fluorescence quenching effect at 460nm after the reaction was also enhanced (as shown in FIG. 4), and the ratio of the fluorescence intensities at 420nm and 460nm was decreased. This indicates that hypochlorite (ClO) can be added in the pH range of 8.0-9.0 - ) The reaction with dopamine functionalized fluorescent carbon dots (DA-dots) prepared in example 1 achieved a fluorescence quenching effect.
(2) Influence of temperature during detection
FIG. 5 shows the dopamine functionalized fluorescent carbon dots (DA-dots) (a) prepared in example 1 and hypochlorite (ClO) added thereto at different temperatures under excitation of 460nm - ) Fluorescence emission spectrum intensity of the latter (b). 3 parts of 10. mu.L solution having pH of 8.0 prepared from the dopamine-functionalized fluorescent carbon dots (DA-dots) prepared in example 1 were added with 50. mu.M hypochlorite (ClO) - ) After 5min of reaction, fluorescence emission spectrum detection is carried out under the excitation of wavelength of 285nm at 25 ℃, 37 ℃ and 50 ℃ respectively. Hypochlorite (ClO) was added as the detection temperature increased from 25 ℃ to 50 ℃ - ) The fluorescence intensity at 420nm before and after the reaction was hardly affected, while the fluorescence intensity at 460nm was measured by adding hypochlorite (ClO) at three temperatures - ) The fluorescence intensity is reduced after the reaction, the fluorescence quenching effects at different temperatures are basically consistent, and the ratio of the fluorescence intensity at 420nm to the fluorescence intensity at 460nm is similar. This indicates that hypochlorite (ClO) can be added at a detection temperature in the range of 25 to 50 deg.C - ) The reaction with the dopamine-functionalized fluorescent carbon dots (DA-dots) prepared in example 1 achieved a fluorescence quenching effect.
(3) Detecting the Effect of reaction time
FIG. 6 shows the addition of hypochlorite (ClO) to the fluorescence Probe (Probe) of the dopamine-functionalized fluorescent carbon dots (DA-dots) prepared in example 1 under the excitation of 460nm - ) The intensity of fluorescence emission spectra after different times of post-reaction. 6 parts of the dopamine-functionalized fluorescent carbon dot (DA-dots) fluorescent Probe (Probe) prepared in example 1 was prepared to have a pH of 8.0 and a concentration of 10. mu.L, and 50. mu.M hypochlorite (ClO) was added to the solution - ) The reactions were carried out, and fluorescence emissions after the reactions were measured for 0s, 50s, 100s, 150s, 200s, and 250s under excitation at a wavelength of 285nm, respectively, and the results are shown in FIG. 6. Hypochlorite (ClO) was added as the reaction time was increased from 0s to 250s - ) The fluorescence intensity at 420nm before and after the reaction is hardly affected, while the fluorescence intensity at 460nm is affected by the addition of hypochlorite (ClO) - ) The fluorescence intensity after the reaction is reduced, the fluorescence quenching effects at different temperatures are basically consistent, and the ratio of the fluorescence intensity at 420nm to the fluorescence intensity at 460nm is similar. This demonstrates the addition of hypochlorite (ClO) to the fluorescent probes (probes) of dopamine-functionalized fluorescent carbon dots (DA-dots) - ) The reaction immediately thereafter, and the change in fluorescence intensity was not affected by the reaction time, indicating that the dopamine-functionalized fluorescent carbon dots (DA-dots) were used as hypochlorite (ClO) - ) The detection reagent has higher detection speed.
FIG. 7A is a graph showing the addition of hypochlorite (ClO) at various concentrations to the fluorescence Probe (Probe) for dopamine-functionalized fluorescent carbon dots (DA-dots) prepared in example 1 - ) The change of the after-fluorescence emission spectrum, B is the ratio of the fluorescence intensity (I) 460nm /I 420nm ) Is added correspondinglyHypochlorite (ClO) - ) A linear fit curve of concentration. The dopamine-functionalized fluorescent carbon dots (DA-dots) prepared in example 1 were formulated to form a solution having a pH of 8.0 and a concentration of 10. mu.L, to which various hypochlorite ions (ClO) were added - ) Detection of the addition of different hypochlorite ions (ClO) - ) As a result of fluorescence emission spectra (emission wavelength 285nm) at concentrations (0. mu.M, 2. mu.M, 5. mu.M, 10. mu.M, 15. mu.M, 20. mu.M, 30. mu.M, 35. mu.M, 40. mu.M, 50. mu.M, and 60. mu.M), as shown in A of FIG. 7, the fluorescence intensity at 420nm did not substantially change, and the fluorescence intensity at 460nm varied with hypochlorite (ClO) - ) The concentration increases and decreases. The ratio of the fluorescence intensity at 460nm to that at 420nm (I) on each of the fluorescence emission curves 460nm /I 420nm ) With corresponding addition of hypochlorite (ClO) - ) The line graph of the concentration is shown as B in FIG. 7, from which it can be seen that the ratio (I) 460nm /I 420nm ) With hypochlorite (ClO) - ) The concentration (c, in μ M) has a good linear relationship and is fitted linearly to give a linear fit equation: i is 460nm /I 420nm -0.023c +2.09, linear correlation coefficient (r) 0.991, linear range 2-60 μ M, detection limit 0.6 μ M. With hypochlorite (ClO) of the prior art - ) Detection method (see Table 3) in comparison, the dopamine functionalized fluorescent carbon dots (DA-dots) prepared by the invention are used for detecting hypochlorite (ClO) - ) The method has wider detection range and lower detection limit.
TABLE 3 different hypochlorite (ClO) - ) Detection result of detection method
Wherein method 1 is from Wei, Z.; li, H.; liu, S., et al, carbon dots as fluorescent/colorimetric probes for real-time detection of hypochlorites and ascorbic acid in cells and body fluids [ J]Anal. chem.,2019,91(24): 15477-15483; method 2 is from Wang, x.; tang, h.; tian, X, et al, Sunlight and UV drive synthesis of Ag nanoparticles for fluorometer and colorimetric dual-mode Sensing of ClO - [J]Spectrochim.acta.a.,2020,229: 117996; method 3 is from Wang, l.; li, B.; jiang, C, et al. A boot based fluorescent probe for the rapid detection of hypochlorites [ J ]]J.Fluoresc, 2018,28(4): 933-941; method 4 was from Kim, p.a.; choe, d.; so, H, et al.A selective fluorescence sensor for hypochlorite use for the detection of hypochlorite in zebrafish [ J]Spectrochim.acta.a.,2021,261: 120059; method 5 is from Taheri, m.; mansource, N.functional silicon nanoparticles as fluorescent probe for detection of hypochlorite in water [ J]J.photochem.photobiol.a,2019,382: 111906; method 6 from Wu, h; zhang, w.; wu, Y, et al, A7-diammineocoumarin-based chemosensor with barbituric acid for hydrochloride and hydrazine [ J]Microchem.j.,2020,159: 105461; method 7 was from Liu, m.; bai, y.; he, Y, et al, simple microwave-assisted synthesis of Ti 3 C 2 MXene quantum dots for ratiometric fluorescence detection of hypochlorite[J]Microchim. acta,2021,188(1) 1-8; method 8 is from Li, y; he, y.; ge, Y, et al, smartphone-associated visual ratio-fluorescence detection of low chloride based on coater nanoparticles [ J]Acta a mol.biomol.spectrosc.,2021,255: 119740; method 9 is from Zhan, y.; luo, f.; guo, L., et al, preparation of an effective ratio fluorescent nanoprobe (m-CDs @ [ Ru (bpy)) 3] 2+ )for visual and specific detection of hypochlorite on site and in living cells[J].ACS Sens.,2017,2(11):1684-1691。
FIG. 8 is a graph showing the concentration-to-fluorescence intensity ratios (I) of various substances added to the fluorescence Probe (Probe) of the dopamine functionalized fluorescent carbon dots (DA-dots) prepared in example 1 460nm /I 420nm ) The influence of (c). The dopamine functionalized fluorescent carbon dots (DA-dots) prepared in example 1 were prepared into 20 parts of a 10. mu.L solution with pH 8.0, to which 19 parts of 50. mu.M Sulfate (SO) was added 4 2+ ) Chloride ion (Cl) - ) Nitrate ion (NO) 3 - ) Sulfur ion (S) 2- ) Carbonate ion (CO) 3 2- ) Magnesium ion (Mg) 2+ ) Barium, bariumIon (Ba) 2+ ) Silver ion (Ag) + ) Iron ion (Fe) 3+ ) Calcium ion (Ca) 2+ ) Hexavalent chromium ion (Cr) 6+ ) Trivalent chromium ion (Cr) 3+ ) Mercury ion (Hg) + ) Hydrogen peroxide (H) 2 O 2 ) And hypochlorite (ClO) - ) After the addition, the fluorescence emission spectra of the small test sample are excited at the wavelength of 285nm at the temperature of 25 ℃ and the same as that of the dopamine functional fluorescent carbon dot (DA-dots) solution without the addition, and the fluorescence intensities at the positions of 420nm and 460nm are recorded to obtain the corresponding fluorescence intensity ratio (I) 460nm /I 420nm ) As shown in fig. 8. As is clear from FIG. 8, among the various ions and compounds used above, only hypochlorite (ClO) was present - ) The fluorescence intensity ratio (I) of the fluorescence Probe (Probe) capable of making dopamine functional fluorescence carbon dots (DA-dots) added 460nm /I 420nm ) The decrease indicates that the dopamine functionalized fluorescent carbon dots (DA-dots) prepared by the invention can be used as ratiometric probes for hypochlorite (ClO) - ) Has good selectivity.
Detection of hypochlorite (ClO) as ratiometric Probe in practice for evaluation of dopamine functionalized fluorescent carbon dots (DA-dots) - ) The effect of (2) carrying out the standard addition recovery experiment specifically is as follows: to the same tap water were added hypochlorite (ClO) at 5. mu.M, 20. mu.M and 50. mu.M, respectively - ) 10 μ L of dopamine-functionalized fluorescent carbon dots (DA-dots) were added, and 3 replicates of each group were run according to the above fluorescence intensity ratio (I) 460nm /I 420nm ) And fitting the equation to calculate the hypochlorite (ClO) obtained by the test - ) The results are shown in Table 4. The recovery rate of the added standard is 98.70% 103.20%, and the Relative Standard Deviation (RSD) is lower than 5%. Thus, the dopamine functionalized fluorescent carbon dots (DA-dots) prepared by the invention are proved to be used as a ratio fluorescent probe for hypochlorite (ClO) - ) The detection has high accuracy, namely, the dopamine functionalized fluorescent carbon dots (DA-dots) as a ratiometric fluorescent probe can be used for detecting hypochlorite (ClO) in practical application - )。
TABLE 4 detection of hypochlorite (ClO) by dopamine functionalized fluorescent carbon dots (DA-dots) in practical application - ) Results
Hypochlorite (ClO) in tap water - ) At a concentration of 3.68M
In conclusion, the invention discloses a novel preparation method of dopamine functional fluorescent carbon dots, which is mainly used for reacting fluorescent carbon dots (C-dots) with dopamine to obtain dopamine functional fluorescent carbon dots (DA-dots). The invention also discloses a novel dopamine functional fluorescent carbon dot (DA-dots) which has double emission peaks at the wavelengths of 420nm and 460 nm. The dopamine-functionalized fluorescent carbon dots (DA-dots) of the present invention contain a phosphate ester bond and are substituted with hypochlorite (ClO) - ) After oxidation, the fluorescence intensity at 460nm wavelength is reduced, while the fluorescence intensity at 420nm wavelength is not affected; simultaneously with hypochlorite (ClO) - ) The concentration is increased, and the fluorescence intensity ratio of the dopamine functional fluorescent carbon dots (DA-dots) at the 420nm and 460nm wavelength is reduced, so that a fluorescence ratio method for detecting the dopamine functional fluorescent carbon dots (DA-dots) can be established, and the method has the advantages of high sensitivity, good accuracy and good selectivity.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (9)
1. A novel preparation method of dopamine functional fluorescent carbon dots is characterized by comprising the following steps:
mixing the fluorescent carbon dots and dopamine in water, adding a buffer solution to adjust the pH value to 8.0, and reacting at 20-35 ℃ for 3-10min to obtain the dopamine-functionalized fluorescent carbon dots.
2. The preparation method according to claim 1, wherein the volume ratio of the fluorescent carbon dot, the dopamine aqueous solution and the water is 200:120-180: 400-500;
the concentration of the dopamine aqueous solution is 1 mM.
3. The method of claim 2, wherein the fluorescent carbon dots are prepared as follows:
(1) dissolving 3-hydroxyphenylboronic acid in water, adjusting the pH to 9.0, and stirring to fully dissolve the 3-hydroxyphenylboronic acid;
(2) filling nitrogen into the solution dissolved in the step (1) to remove oxygen in the solution, filling the solution into a reaction kettle, and reacting for 6-10h at the temperature of 150-;
(3) and after the reaction is finished, cooling to room temperature, centrifuging, and taking supernatant fluid to obtain the fluorescent carbon dots.
4. The method according to claim 3, wherein the mass-to-volume ratio of the 3-hydroxyphenylboronic acid to the water is 0.15 to 0.25:20 to 25, g: mL.
5. The method of claim 3, wherein the pH is adjusted by using NaOH solution having a concentration of 0.1 to 0.2M.
6. The method as claimed in claim 3, wherein the centrifugation is carried out at 9000-12000rpm for 8-15 min.
7. The method according to claim 1, wherein the buffer solution is a phosphate buffer solution having a concentration of 40 mM.
8. The dopamine-functionalized fluorescent carbon dot prepared by the preparation method according to any one of claims 1 to 7.
9. Use of the dopamine-functionalized fluorescent carbon dot of claim 8 in the preparation of a ratiometric fluorescent probe for detecting hypochlorite.
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