CN115124997A - Preparation of carbon quantum dot fluorescent probe and application of carbon quantum dot fluorescent probe in detection of iron ions and cysteine - Google Patents
Preparation of carbon quantum dot fluorescent probe and application of carbon quantum dot fluorescent probe in detection of iron ions and cysteine Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 117
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 title claims description 13
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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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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- G01N21/64—Fluorescence; Phosphorescence
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Abstract
The invention provides a preparation method of a carbon quantum dot fluorescent probe, which comprises the steps of dissolving tryptophan in deionized water, carrying out ultrasonic stirring uniformly to obtain a tryptophan solution, and reacting the tryptophan solution at 180-200 ℃ for 120-150 minutes; filtering by using 0.22 mu m of filter paper after the reaction is finished, removing unreacted solid particles, and repeating for 5-6 times to obtain a clear golden yellow solution; and (3) dialyzing after rotary evaporation, dialyzing for 20-24 h by using a 500-1000 Da cellulose dialysis membrane, and then freeze-drying to obtain the carbon quantum dot fluorescent probe CQDs. Simple preparation, short reaction time and no pollutionAny organic matter is used, the raw materials are cheap, and the traditional Chinese medicine has no toxic or side effect on human bodies. The carbon quantum dot fluorescent probe can be used for detecting Fe with high selectivity 3+ And can also detect Fe 3+ On the basis of the above, Cys is continuously detected with high selectivity.
Description
Technical Field
The invention belongs to the technical field of synthesis and application of carbon materials, and particularly relates to a preparation method of a carbon quantum dot fluorescent probe.
Background
All carbon-based dot-like nano materials can be called carbon quantum dot CQDs (carbon quantum dots) which are different from the materials in the previous carbon family, are usually nano-sized, are quasi-zero-dimensional (the size of three dimensions is in the range of 1-100 nm), have excellent optical performance mainly caused by quantum confinement effect and boundary effect, and have good biocompatibility, good water solubility, stable fluorescence intensity and most important low toxicity. The attractive properties of CQDs have made them attractive to researchers in bioimaging, chemosensing, and the like.
Common quantum dots fall into two categories: one class is that heavy metals such as CdS, CdTe quantum dots, etc. as raw materials are limited due to their own toxicity; the other type of carbon quantum dots CQDs which take carbon base as raw materials have rich precursors and wide raw material sources, mainly comprise micromolecular organic matters and biomass materials, and according to the existing research, crayfish shells, onions, honey, cucumbers, rice, cigarette ash, garbage and the like can be used as the raw materials of the carbon-based CQDs. The optical property is stable, and the fluorescent powder can be maintained in a certain fluorescence intensity range for a long time in an aqueous solution.
The carbon quantum dot fluorescent probe has immeasurable effect on detecting pesticide residue, pesticide, food additive, ions and amino acid. The carbon quantum dot fluorescent probe structurally comprises a fluorophore, a linking group and a recognition group, and the recognition group is usually used for detection. The methods for identifying ions and amino acids include gas-liquid chromatography, electrochemical sensing signal method, colorimetric method and fluorescent probe method. Most rely on large instruments, and although accurate results can be obtained, the sample is often high in requirements, time-consuming, labor-consuming, expensive, and incapable of obtaining identification results quickly. Therefore, the fluorescent probe method has the characteristics of prominent effect, various signal output modes, high sensitivity, real-time analysis, simplicity, convenience and rapidness.
Iron itself is not toxic, but iron poisoning may also result when excessive iron preparations are ingested or taken by mistake, and iron deficiency anemia, pale skin, painful tongue, fatigue or weakness, poor appetite, nausea, and other symptoms may occur when a person is iron deficiency. Cysteine (Cys) is an amino acid having physiological functions, is the only amino acid having a reducing group of mercapto (-SH) among 20 kinds of amino acids constituting proteins, and is also an amino acid-based antidote, which participates in the reduction process of cells and phospholipid metabolism in the liver, has a pharmacological effect of protecting liver cells from being damaged, and promoting liver function recovery and exuberance. It is mainly used for treating radiopharmaceuticals poisoning, heavy metal poisoning, and antimonide poisoning, and can also be used for treating hepatitis, toxic hepatitis, seropathy, etc., and preventing liver necrosis. Too much or too little iron and cysteine content in the human body affects the health of the body, so a rapid and low-toxicity or even non-toxic detection is essential.
Li Ming et al discloses an invention patent (CN 110982518A) "A N-S codoped carbon quantum dot fluorescent probe for cysteine detection and its preparation and application", mixing ethylenediamine, deionized water and DTNB at room temperature, carbonizing at 160-Source mixing to obtain Pd 2+ /NS-CQDs for detecting cysteine in water samples. The method has the advantages of simple preparation method, high sensitivity, good reproducibility and the like, has higher selectivity to the cysteine, and effectively reduces the interference of other ions or amino acids.
Chenshujuan et al discloses (CN 112852420A) "a carbon quantum dot fluorescent probe and a method for detecting thiamphenicol content", which comprises pulverizing crayfish shell, dispersing in deionized water, mixing with cysteine, carbonizing at 200 deg.C for 8h by hydrothermal method, filtering, centrifuging, purifying, and freeze-drying to obtain carbon quantum dot. Through static quenching, the method can be well applied to the rapid detection of trace thiamphenicol residues in foods and living cells.
Gao Da Ming et al discloses (CN 109054822A) "A preparation method of carbon quantum dot fluorescent probe for paraquat detection", which comprises placing m-phenylenediamine in anhydrous ethanol, dissolving, transferring to a reaction kettle, reacting at 160 deg.C for 12 h, cooling, adding developing agent, separating by chromatography, and dialyzing to obtain carbon quantum dot fluorescent probe with surface rich in hydroxyl and carbonyl. The carbon quantum dots with negative electricity on the surface and the target paraquat with positive electricity generate fluorescence resonance energy transfer through the interaction of anions and cations, so that the fluorescence intensity is reduced, and the selective detection of the target molecule paraquat is realized.
The above-mentioned inventions have all advantages, but basically all have the disadvantages of many required raw materials, most organic substances, certain stimulation to skin and respiratory tract, long reaction time and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon quantum dot fluorescent probe, and the prepared carbon quantum dot fluorescent probe has the advantages of wide raw material source, low price, low toxicity and good biocompatibility, and can be finally used for rapidly and continuously identifying Fe 3+ And Cys.
Preparation of carbon quantum dot fluorescent probe
The preparation method of the carbon quantum dot fluorescent probe comprises the following process steps:
(1) dissolving tryptophan (Trp) serving as a carbon source in 70 mL of deionized water, and performing ultrasonic stirring to obtain a tryptophan solution; reacting the tryptophan solution at 180-200 ℃ for 120-150 minutes; wherein the concentration of the tryptophan solution is 0.05-1.00 mol/L.
(2) Filtering by using 0.22 mu m of filter paper after the reaction is finished, removing unreacted solid particles, and repeating for 5-6 times to obtain a clear golden yellow solution; performing dialysis after rotary evaporation, performing dialysis for 20-24 h by using a 500-1000 Da cellulose dialysis membrane, performing freeze drying for 18-24 h at-20 to-30 ℃ to obtain pale yellow fluffy solid powder CQDs, and finally preparing the solution to obtain a CQDs fluorescent probe for subsequent Fe 3+ And testing for Cys.
FIG. 1 is a high resolution transmission electron micrograph of CQDs. As can be seen from the figure, CQDs are spherical, uniformly distributed without agglomeration, and have an average particle size of 2.7. + -. 0.2 nm. FIG. 2 is a partial enlarged view of CQDs under high resolution transmission electron microscopy, showing that CQDs have lattice striations of about 0.21 nm.
FIG. 3 is a UV-Vis spectrum and a fluorescence test chart of CQDs. It can be seen in the uv-map that there are two distinct absorption peaks at 218 nm and 280 nm, the strong absorption peak at 218 nm being attributed to the transition of C = C bonds pi-pi, and the relatively weak peak at 280 nm being attributed to the transition of C = O bonds n-pi.
As can be seen in the fluorescence plot of FIG. 3, the maximum excitation wavelength of CQDs is 370 nm and the maximum emission wavelength is 445 nm. The picture is a real picture of CQDs under the irradiation of an ultraviolet lamp and a fluorescent lamp, wherein the ultraviolet lamp emits blue fluorescence, and the fluorescent lamp emits light yellow transparent solution.
Second, carbon quantum dot fluorescent probe pair Fe 3+ And detection of Cys
1. Carbon quantum dot fluorescent probe pair Fe 3+ Detection of (2)
(1) 2mL of CQDs solution with the concentration of 1 mu g/mL is placed in a cuvette, and is irradiated to blue fluorescence under an ultraviolet lamp (365 nm), and then a fluorescence spectrophotometer is used for testing, wherein the testing condition is fixed to be 3 nm of a slit, and the excitation wavelength is 370 nm. Note F 0 CQDs fluorescence intensity. And studied different speciesQuenching capability of metal ions on CQDs, and adding 30 muL Fe into 2mL CQDs solution (1 mug/mL) 3+ ，Mg 2+ ，Mn 2+ ，Li 2+ ，Ca 2+ ，Cd 2+ ，Fe 2+ ，Cu 2+ ，Ni 2+ ，Co 2+ ， Pb 2+ Is (100. mu. mol/L). The fluorescence intensity obtained by F measurement was measured at a wavelength of 370 nm with the slit fixed at 3 nm, and the fluorescence measurement is shown in FIG. 4, in which only Fe is observed 3+ Can quench the fluorescence of CQDs, and the quenching capability of other 10 ions to CQDs is very little, which shows that CQDs can efficiently detect Fe in aqueous solution 3+ The inset is a real picture taken under an ultraviolet lamp, consistent with the test results.
CQDs, Fe with concentration of 1 mug/mL is prepared 3+ The concentration range of the ions is 0-400 mu M, 2mL of CQDs are added into the cuvette as a main solution, and 30 mu L of Fe with different concentrations are added subsequently 3+ After mixing for 5 min, the test was carried out uniformly at an excitation wavelength of 370 nm. In FIG. 5 with Fe 3+ The increase in concentration, the gradual decrease in fluorescence at 445 nm, indicates Fe 3+ Can effectively quench the fluorescence intensity of CQDs. As can be seen in FIGS. 6 and 7, Fe 3+ The concentration has better linear relation in the range of 0-10 mu M and 10-100 mu M, the linear relation of 0-10 mu M is y = -3026x +61514, R 2 =0.9903 where x represents Fe 3+ In μ M, y represents the fluorescence intensity; the linear relation of 10-100 mu M is y = -303x +36917, R 2 =0.9859 where x represents Fe 3+ The concentration of (2) was calculated in the unit of. mu.M, and y represents the fluorescence intensity, and the minimum concentration was calculated to be 1.21. mu.M.
2. Continuous monitoring of Cys by carbon quantum dot fluorescence probe
To 2mL of CQDs solution (1. mu.g/mL), 30. mu.L of Fe was added 3+ Aqueous solution of (100. mu. mol/L), Fe 3+ Quenching the fluorescence of CQDs; to CQDs/Fe, respectively 3+ Adding 30 μ L cysteine Cys, tartaric acid Tar, methionine Met, lysine Lys, serine Ser, proline Pro, histidine His, tyrosine Tyr, and milkAcid La, phenylalanine Phe, mandelic acid Man, tryptophan Trp and glutamic acid Glu solution (200 mu mol/L). The fluorescence test was carried out with the slit fixed at 3 nm and the excitation wavelength at 370 nm, as shown in FIG. 8, it can be seen from FIG. 8 that only Cys enables CQDs/Fe 3+ While the addition of other amino acid solutions did not result in CQDs/Fe 3+ The fluorescence of CQDs is obviously changed, which shows that CQDs can efficiently detect Cys in aqueous solution.
CQDs with the concentration of 1 mug/mL is prepared, the concentration range of Cys is 0-200 mug M, 2mL of CQDs is added into a cuvette to serve as a main solution, 30 muL of Cys with different concentrations are added subsequently and mixed for 5 min, and then the CQDs are tested under the condition that the excitation wavelength is 370 nm. CQDs/Fe in FIG. 9 with increasing Cys concentration from 0-200. mu.M 3+ The fluorescence intensity is gradually increased around 445 nm, which shows that the CQDs/Fe can be effectively recovered by adding Cys 3+ Fluorescence of (2). As can be seen in FIGS. 10 and 11, there is a good linear relationship between the range of 3-10 μ M and 10-50 μ M, the linear relationship of 3-10 μ M being y =1181x-3696, R 2 =0.9960 where x denotes concentration of Cys in μ M and y denotes fluorescence intensity; the linear relationship of 10-50 μ M is y =707x-455, R 2 =0.9978, where x represents the concentration of Cys in μ M and y represents the fluorescence intensity, the lowest detected concentration was calculated to be LOD =1.10 μ M.
3. Mechanism of detection
Detection of Fe for the study of CQDs 3+ The quenching mechanism, the change of UV-vis spectrum was studied. When CQDs is added with Fe 3+ Then, Fe 3+ Has strong electron affinity and a hollow orbit, while the surface of CQDs has nitrogen, oxygen and other functional groups, lone pair electrons and Fe 3+ Can coordinate with the fluorescent material quickly, and form a non-luminous complex by combination so as to quench fluorescence. As can be seen in fig. 12, the UV-vis spectrum of CQDs changed significantly, the peak at 290 nm shifted significantly red, and the absorption peak at 218 nm for the C = C bond disappeared. These results show that Fe 3+ The presence of CQDs affects the surface state of CQDs due to quenching of fluorescence by the CQDs due to static quenching. In addition, it can be found from the observation of FIG. 13 that the excitation of CQDsAnd emission spectrum with Fe 3+ Overlap of the absorption peaks in the UV-Vis absorption spectra of (A), indicating that the fluorescence of CQDs is overlapped by Fe 3+ Screening, i.e. fluorescence of CQDs by Fe 3+ Quenching, which is caused by the IFE fluorescence phenomenon. Thus, CQDs detection of Fe was obtained 3+ Quenching is caused by the combination of static quenching and the IFE fluorescence phenomenon. Understanding the mechanism may allow us to understand the thing itself more thoroughly, and the efficient IFE phenomenon indicates that its absorption spectrum overlaps with the excitation or emission of the fluorophore with sufficient spectral overlap. When Cys is subsequently added, due to-SH and Fe 3+ Is relatively strong, so that when Cys containing-SH group appears in the solution, Fe 3+ Preferentially bind to Cys, resulting in Fe 3+ Released from the CQDs surface, and finally the fluorescence of the CQDs surface is restored.
Compared with the prior art, the invention has the advantages that:
according to the invention, the carbon quantum dot fluorescent probe with blue fluorescence can be obtained by using tryptophan as a carbon source and carbonizing at 180-200 ℃ for 120-150 min, and the method has the advantages of simple preparation, short reaction time, no use of any organic matter, low price of raw materials and no toxic or side effect on human bodies. In addition, the carbon quantum dot fluorescent probe can detect Fe with high selectivity 3+ And can also detect Fe 3+ On the basis of the above, Cys is continuously detected with high selectivity.
Drawings
FIG. 1 is a high resolution transmission electron micrograph of CQDs (the inset is the statistical distribution of their particle sizes).
FIG. 2 is a partial magnified view of CQDs by high resolution transmission electron microscopy (the inset shows the lattice fringes).
FIG. 3 is a diagram showing an ultraviolet-visible spectrum and a fluorescence excitation and emission spectrum of CQDs (the inset is a photograph of a CQDs taken by a real object under a fluorescent lamp and an ultraviolet lamp).
FIG. 4 is the fluorescence spectrum of CQDs fluorescent probe detecting 11 ions (the inset is the photograph of the real object under fluorescent lamp).
FIG. 5 is Fe 3+ Concentration versus fluorescence intensity of CQDs.
FIG. 6 is Fe 3+ Concentration (0-10. mu.M) and CQDs fluorescence intensity.
FIG. 7 is Fe 3+ Concentration (10-100. mu.M) and CQDs fluorescence intensity.
FIG. 8 is the fluorescence spectrum of the CQDs fluorescent probe for detecting 13 amino acids (the inset is the photograph of the real object under fluorescent lamp).
FIG. 9 is a graph of Cys concentration versus CQDs fluorescence intensity.
FIG. 10 is a graph of the linear relationship between Cys concentration (3-10. mu.M) and CQDs fluorescence intensity.
FIG. 11 is a linear plot of Cys concentration (10-50. mu.M) versus CQDs fluorescence intensity.
FIG. 12 shows CQDs and CQDs + Fe 3+ Ultraviolet-visible absorption spectrum of (a).
FIG. 13 is Fe 3+ Ultraviolet-visible absorption spectra of CQDs, excitation and emission spectra of CQDs.
Detailed Description
The preparation and application of the CQDs fluorescent probe of the present invention are further illustrated by the following specific examples. The implementation is carried out on the premise of the technical scheme of the invention, and a detailed implementation method and a specific operation process are provided.
EXAMPLE 1 preparation of carbon Quantum dot fluorescent probes
(1) Dissolving 0.51g of tryptophan in 70 mL of deionized water, and uniformly stirring by ultrasonic waves to obtain a tryptophan solution.
(2) And (2) putting the tryptophan solution obtained in the step (1) into a reaction kettle with a polytetrafluoroethylene lining, and reacting at 180 ℃ for 120 minutes.
(3) And (3) filtering the reactant in the step (2) by using 0.22 mu m of filter paper, removing unreacted solid particles, and repeating for 5-6 times to obtain a clear golden yellow solution.
(4) And (4) dialyzing the solution in the step (3) for 18h by using a 500-1000 Da cellulose dialysis membrane.
(5) And (4) after the solution in the step (4) is dialyzed, freezing and drying for 18 hours at the temperature of minus 20 ℃ to obtain light yellow fluffy solid powder which is CQDs. 0.025 g of CQDs is weighed, dissolved by deionized water, transferred to a 25 mL volumetric flask to prepare a solution of 1 mg/mL, and then diluted to 1 mug/mL for subsequent testing.
EXAMPLE 2 preparation of carbon Quantum dot fluorescent probes
(1) Dissolving 1.02g of tryptophan in 70 mL of deionized water, and uniformly stirring by ultrasonic waves to obtain a tryptophan solution.
(2) And (2) putting the tryptophan solution obtained in the step (1) into a reaction kettle with a polytetrafluoroethylene lining, and reacting for 120 minutes at 200 ℃.
(3) And (3) filtering the reactant in the step (2) by using 0.22 mu m filter paper, removing unreacted solid particles, and repeating for 5-6 times to obtain a clear golden yellow solution.
(4) And (4) dialyzing the solution in the step (3) for 20h by using a 500-1000 Da cellulose dialysis membrane.
(5) And (5) freeze-drying the solution obtained in the step (4) at the temperature of minus 25 ℃ for 20 hours to obtain light yellow fluffy solid powder which is CQDs.
EXAMPLE 3 preparation of carbon Quantum dot fluorescent probes
(1) Dissolving 2.04 g of tryptophan in 70 mL of deionized water, and uniformly stirring by ultrasonic waves to obtain a tryptophan solution.
(2) And (2) putting the tryptophan solution obtained in the step (1) into a reaction kettle with a polytetrafluoroethylene lining, and reacting for 150 minutes at 200 ℃.
(3) And (3) filtering the reactant in the step (2) by using 0.22 mu m filter paper, removing unreacted solid particles, and repeating for 5-6 times to obtain a clear golden yellow solution.
(4) And (4) dialyzing the solution in the step (3) for 24 hours by using a 500-Da cellulose dialysis membrane.
(5) And (4) carrying out freeze drying on the solution in the step (4) at the temperature of-30 ℃ for 24 hours to obtain light yellow fluffy solid powder which is CQDs.
Example 4 carbon Quantum dot fluorescent Probe for Fe 3+ Detection of (2)
To 2mL of CQDs solution (1. mu.g/mL), CQDs were added separately30 μ L of Fe 3+ ，Mg 2+ ，Mn 2+ ，Li 2+ ，Ca 2+ ，Cd 2+ ，Fe 2 + ，Cu 2+ ，Ni 2+ ，Co 2+ ， Pb 2+ Is (100. mu. mol/L). If the fluorescence of CQDs is quenched, it indicates that Fe is added 3+ (ii) a If the fluorescence of CQDs does not change significantly, it indicates that other metal ions are added.
Example 5 continuous detection of Cys by carbon Quantum dot fluorescent probes
To 2mL of CQDs solution (1. mu.g/mL), 30. mu.L of Fe was added 3+ Aqueous solution (100. mu. mol/L), Fe 3+ Quenching the fluorescence of CQDs; then respectively to CQDs/Fe 3+ Adding 30 μ L cysteine Cys, tartaric acid Tar, methionine Met, lysine Lys, serine Ser, proline Pro, histidine His, tyrosine Tyr, lactic acid La, phenylalanine Phe, mandelic acid Man, tryptophan Trp, glutamic acid Glu solution (200 μmol/L), if CQDs/Fe 3+ The fluorescence of (2) is turned back on, indicating that cysteine Cys was added; if CQDs/Fe 3+ The fluorescence of (2) did not change significantly indicating that additional amino acids were added.
Claims (7)
1. A preparation method of a carbon quantum dot fluorescent probe comprises the following process steps:
(1) dissolving tryptophan in deionized water, carrying out ultrasonic stirring uniformly to obtain a tryptophan solution, and reacting the tryptophan solution at 180-200 ℃ for 120-150 minutes;
(2) filtering by using 0.22 mu m of filter paper after the reaction is finished, removing unreacted solid particles, and repeating for 5-6 times to obtain a clear golden yellow solution; dialyzing after rotary evaporation for 20-24 h by using a 500-1000 Da cellulose dialysis membrane; and then freeze-dried to give a pale yellow fluffy solid powder CQDs.
2. The method for preparing a carbon quantum dot fluorescent probe according to claim 1, wherein the method comprises the following steps: in the step (1), the concentration of the tryptophan solution is 0.05-1.00 mol/L.
3. The method for preparing a carbon quantum dot fluorescent probe according to claim 1, wherein the method comprises the following steps: in the step (2), the freeze drying is carried out for 18-24 h at-20 to-30 ℃.
4. Detection of Fe by carbon quantum dot fluorescent probe prepared by the method of claim 1 3+ The use of (1).
5. The method for detecting Fe by using the carbon quantum dot fluorescent probe as claimed in claim 4 3+ The application of (1), which is characterized in that: adding Fe to CQDs solution 3+ ，Mg 2+ ，Mn 2+ ，Li 2+ ，Ca 2+ ，Cd 2+ ，Fe 2+ ，Cu 2+ ，Ni 2+ ，Co 2+ ， Pb 2+ Of an aqueous solution of (1), only Fe 3+ Can quench the fluorescence of CQDs.
6. The method of claim 1, wherein the carbon quantum dot fluorescent probe is used for continuously detecting Fe 3+ And application in cysteine.
7. The carbon quantum dot fluorescent probe as claimed in claim 6 for continuously detecting Fe 3+ The application of cysteine is characterized in that: adding Fe to CQDs solution 3+ ，Mg 2+ ，Mn 2+ ，Li 2+ ，Ca 2+ ，Cd 2+ ，Fe 2+ ，Cu 2+ ，Ni 2+ ，Co 2+ ，Pb 2+ Aqueous solution of (1), only Fe 3+ Quenching the fluorescence of CQDs; CQDs/Fe quenched toward fluorescence respectively 3+ Adding cysteine Cys, tartaric acid Tar, methionine Met, lysine Lys, serine Ser, proline Pro, histidine His, tyrosine Tyr, lactic acid La, phenylalanine Phe, mandelic acid Man, tryptophan Trp, and glutamic acid Glu solution, wherein only the addition of cysteine can make CQDs/Fe 3+ The fluorescence of (2) is recovered.
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