Ammonium Pyrrolidine Dithiocarbamate-Modified CdTe/CdS Quantum Dots as a Turn-on Fluorescent Sensor for Detection of Trace Cadmium Ions
<p>The reaction mechanism of the turn-on mode CdTe/CdS quantum dots (QD) sensor.</p> "> Figure 2
<p>(<b>a</b>) Relationship between the fluorescence intensity of a QD solution without etching and time. Concentration of Tris-HCl buffer solution: 10 mmol/L. pH of Tris-HCl buffer solution: 8.5. Concentration of added QD solution: 5 μmol/L. Addition order: Tris-HCl buffer solution (2 mL) → QD solution (0.4 mL) → Tris-HCl buffer solution (1.6 mL). Excitation wavelength: 460 nm. Observation time: 10 min. (<b>b</b>,<b>c</b>) The fluorescence response of a QD solution without etching. Concentration of Tris-HCl buffer solution: 10 mmol/L. pH of Tris-HCl buffer solution: 8.5. Concentration of added QD solution: 5 μmol/L. Addition order: Tris-HCl buffer solution (2 mL) → QD solution (0.4 mL) → Tris-HCl buffer solution (1.6 mL). Excitation wavelength: 460 nm. All data in this figure is mean of five measurements.</p> "> Figure 2 Cont.
<p>(<b>a</b>) Relationship between the fluorescence intensity of a QD solution without etching and time. Concentration of Tris-HCl buffer solution: 10 mmol/L. pH of Tris-HCl buffer solution: 8.5. Concentration of added QD solution: 5 μmol/L. Addition order: Tris-HCl buffer solution (2 mL) → QD solution (0.4 mL) → Tris-HCl buffer solution (1.6 mL). Excitation wavelength: 460 nm. Observation time: 10 min. (<b>b</b>,<b>c</b>) The fluorescence response of a QD solution without etching. Concentration of Tris-HCl buffer solution: 10 mmol/L. pH of Tris-HCl buffer solution: 8.5. Concentration of added QD solution: 5 μmol/L. Addition order: Tris-HCl buffer solution (2 mL) → QD solution (0.4 mL) → Tris-HCl buffer solution (1.6 mL). Excitation wavelength: 460 nm. All data in this figure is mean of five measurements.</p> "> Figure 3
<p>Relationship between the fluorescence intensity of the QD solution and the volume of added ammonium pyrrolidine dithiocarbamate (APDC) solution. Concentration of Tris-HCl buffer solution: 10 mmol/L. pH of Tris-HCl buffer solution: 8.5. Concentration of added QD solution: 5 μmol/L. Concentration of added APDC solution: 100 μmol/L. Addition order: Tris-HCl buffer solution (2 mL) → QD solution (0.4 mL) → APDC solution (0–0.6 mL) → Tris-HCl buffer solution (1.6–1 mL). Excitation wavelength: 460 nm. Observation time: 3 min. All data in this figure is mean of five measurements.</p> "> Figure 4
<p>Relationship between the fluorescence intensity of the QD solution with added cadmium standard and the volume of the added APDC solution. Concentration of Tris-HCl buffer solution: 10 mmol/L. pH of Tris-HCl buffer solution: 8.5. Concentration of added QD solution: 5 μmol/L. Concentration of added APDC solution: 100 μmol/L. Concentration of cadmium standard solution: 1 g/L. Addition order: Tris-HCl buffer solution (2 mL) → QD solution (0.4 mL) → APDC solution (0–0.6 mL) → cadmium standard solution (0.001 mL) → Tris-HCl buffer solution (1.6–1 mL). Excitation wavelength: 460 nm. Observation time: 3 min. All data in this figure is mean of five measurements.</p> "> Figure 5
<p>The fluorescence intensity recovery ratio of the etched QD solution with added cadmium standard. Concentration of Tris-HCl buffer solution: 10 mmol/L. pH of Tris-HCl buffer solution: 8.5. Concentration of added QD solution: 5 μmol/L. Concentration of added APDC solution: 100 μmol/L. Concentration of cadmium standard solution: 1 g/L. Addition order: Tris-HCl buffer solution (2 mL) → QD solution (0.4 mL) → APDC solution (0–0.6 mL) → cadmium standard solution (0.001 mL) → Tris-HCl buffer solution (1.6–1 mL). Excitation wavelength: 460 nm. All data in this figure is mean of five measurements.</p> "> Figure 6
<p>The relationship between the fluorescence intensity recovery ratio and the pH of Tris-HCl buffer solution. Concentration of Tris-HCl buffer solution: 10 mmol/L. Concentration of added QD solution: 5 μmol/L. Concentration of added APDC solution: 100 μmol/L. Concentration of cadmium standard solution: 1 g/L. Addition order: Tris-HCl buffer solution (2 mL) → QD solution (0.4 mL) → APDC solution (0.52 mL) → cadmium standard solution (0.001 mL) → Tris-HCl buffer solution (1.08 mL). Excitation wavelength: 460 nm. All data in this figure is mean of five measurements.</p> "> Figure 7
<p>Relationship between the fluorescence intensity of the QD solution and the time after addition of the APDC solution. Concentration of Tris-HCl buffer solution: 10 mmol/L. pH of Tris-HCl buffer solution: 8.5. Concentration of added QD solution: 5 μmol/L. Concentration of APDC solution: 100 μmol/L. Addition order: Tris-HCl buffer solution (2 mL) → QD solution (0.4 mL) → APDC solution (0.52 mL) → Tris-HCl buffer solution (1.08 mL). Excitation wavelength: 460 nm. Observation time: 35 min. All data in this figure is mean of five measurements.</p> "> Figure 8
<p>Relationship between the fluorescence intensity of the restored QD solution and the time after addition of the cadmium standard solution. Concentration of Tris-HCl buffer solution: 10 mmol/L. pH of Tris-HCl buffer solution: 8.5. Concentration of added QD solution: 5 μmol/L. Concentration of APDC solution: 100 μmol/L. Concentration of cadmium standard solution: 1 g/L. Addition order: Tris-HCl buffer solution (2 mL) → QD solution (0.4 mL) → APDC solution (0.52 mL) → cadmium standard solution (0.001 mL) → Tris-HCl buffer solution (1.08 mL). Excitation wavelength: 460 nm. Observation time: 10 min. All data in this figure is mean of five measurements.</p> "> Figure 9
<p>Relationship between the fluorescence intensity of the restored QD solution and the concentration of added Cd<sup>2+</sup> in the QD solution. Concentration of Tris-HCl buffer solution: 10 mmol/L. pH of Tris-HCl buffer solution: 8.5. Concentration of added QD solution: 5 μmol/L. Concentration of APDC solution: 100 μmol/L. Concentration of cadmium standard solution: 1 g/L. Addition order: Tris-HCl buffer solution (2 mL) → QD solution (0.4 mL) → APDC solution (0.52 mL) → cadmium standard solution (0–0.0028 mL) → Tris-HCl buffer solution (1.08–1.0772 mL). Excitation wavelength: 460 nm. Observation time: 3 min. All data in this figure is mean of five measurements.</p> "> Figure 10
<p>(<b>a</b>) Corresponding calibration plots for the APDC/CdTe/CdS QD solution based on different Cd<sup>2+</sup> concentrations in Tris-HCl buffer solution. Concentration of Tris-HCl buffer solution: 10 mmol/L. pH of Tris-HCl buffer solution: 8.5. Concentration of added QD solution: 5 μmol/L. Concentration of APDC solution: 100 μmol/L. Concentration of cadmium standard solution: 1 g/L. Addition order: Tris-HCl buffer solution (2 mL) → QD solution (0.4 mL) → APDC solution (0.52 mL) → cadmium standard solution (0–0.0004 mL) → Tris-HCl buffer solution (1.08 mL). Excitation wavelength: 460 nm. Observation time: 3 min. * Mean of five measurements. (<b>b</b>) Corresponding calibration plots for the APDC/CdTe/CdS QD solution based on different Cd<sup>2+</sup> concentrations in Tris-HCl buffer solution. Concentration of Tris-HCl buffer solution: 10 mmol/L. pH of Tris-HCl buffer solution: 8.5. Concentration of added QD solution: 5 μmol/L. Concentration of APDC solution: 100 μmol/L. Concentration of cadmium standard solution: 1 g/L. Addition order: Tris-HCl buffer solution (2 mL) → QD solution (0.4 mL) → APDC solution (0.52 mL) → cadmium standard solution (0.0004–0.0024 mL) → Tris-HCl buffer solution (1.08–1.0776 mL). Excitation wavelength: 460 nm. Observation time: 3 min. All data in this figure is mean of five measurements.</p> "> Figure 11
<p>(<b>a</b>,<b>b</b>) Relationship between the fluorescence intensity of the restored QD solution and the presence of added Cd<sup>2+</sup> and other ions in the QD solution. Concentration of Tris-HCl buffer solution: 10 mmol/L. pH of Tris-HCl buffer solution: 8.5. Concentration of added QD solution: 5 μmol/L. Concentration of APDC solution: 100 μmol/L. Concentration of cadmium standard solution: 2.5 mmol/L. Concentration of other standard solutions: 2.5 mmol/L. Addition order: Tris-HCl buffer solution (2 mL) → QD solution (0.4 mL) → APDC solution (0.52 mL) → cadmium standard solution (0.008 mL) → other standard solution (0.008 mL) → Tris-HCl buffer solution (1.064 mL). Excitation wavelength: 460 nm. Observation time: 3 min. All data in this figure is mean of five measurements.</p> "> Figure 12
<p>(<b>a</b>) Relationship between the fluorescence intensity of the restored QD solution and the concentration of thiosemicarbazide (TSC) solution added into a copper standard solution before detection. Concentration of TSC solution: 5–100 mmol/L. Concentration of copper standard solution before detection: 0.5 mol/L. Mix order: copper standard solution (5 μL) → TSC solution (5 mL). Concentration of Tris-HCl buffer solution: 10 mmol/L. pH of Tris-HCl buffer solution: 8.5. Concentration of added QD solution: 5 μmol/L. Concentration of APDC solution: 100 μmol/L. Concentration of cadmium standard solution: 2.5 mmol/L. Concentration of mixed copper standard solution: 0.5 mmol/L. Concentration of TSC in mixed copper standard solution: 5–100 mmol/L. Addition order: Tris-HCl buffer solution (2 mL) → QD solution (0.4 mL) → APDC solution (0.52 mL) → cadmium standard solution (0.008 mL) → mixed copper standard solution (0.04 mL) → Tris-HCl buffer solution (1.032 mL). Excitation wavelength: 460 nm. Observation time: 3 min. * Mean of five measurements. (<b>b</b>) Relationship between the fluorescence intensity of the restored QD solution and the concentration of TSC solution added into a mercury standard solution before detection. Concentration of TSC solution: 5–100 mmol/L. Concentration of mercury standard solution before detection: 0.1 mol/L. Mix order: mercury standard solution (25 μL) → TSC solution (5 mL). Concentration of Tris-HCl buffer solution: 10 mmol/L. pH of Tris-HCl buffer solution: 8.5. Concentration of added QD solution: 5 μmol/L. Concentration of APDC solution: 100 μmol/L. Concentration of cadmium standard solution: 2.5 mmol/L. Concentration of mixed mercury standard solution: 0.5 mmol/L. Concentration of TSC in mixed mercury standard solution: 5–100 mmol/L. Addition order: Tris-HCl buffer solution (2 mL) → QD solution (0.4 mL) → APDC solution (0.52 mL) → cadmium standard solution (0.008 mL) → mixed mercury standard solution (0.04 mL) → Tris-HCl buffer solution (1.032 mL). Excitation wavelength: 460 nm. Observation time: 3 min. All data in this figure is mean of five measurements.</p> "> Figure 13
<p>(<b>a</b>) Relationship between the fluorescence intensity of the restored QD solution and the concentration of TSC solution added into a silver standard solution before detection. Concentration of TSC solution: 5–100 mmol/L. Concentration of silver standard solution before detection: 0.5 mol/L. Mix order: silver standard solution (5 μL) → TSC solution (5 mL). Concentration of Tris-HCl buffer solution: 10 mmol/L. pH of Tris-HCl buffer solution: 8.5. Concentration of added QD solution: 5 μmol/L. Concentration of APDC solution: 100 μmol/L. Concentration of cadmium standard solution: 2.5 mmol/L. Concentration of mixed silver standard solution: 0.5 mmol/L. Concentration of TSC in mixed silver standard solution: 5–100 mmol/L. Addition order: Tris-HCl buffer solution (2 mL) → QD solution (0.4 mL) → APDC solution (0.52 mL) → cadmium standard solution (0.008 mL) → mixed silver standard solution (0.04 mL) → Tris-HCl buffer solution (1.032 mL). Excitation wavelength: 460 nm. Observation time: 3 min. * Mean of five measurements. (<b>b</b>) Relationship between the fluorescence intensity of the restored QD solution and the concentration of (1,2-cyclohexylenedinitrilo)-tetraacetic acid (DCTA) solution added into a zinc standard solution before detection. Concentration of DCTA solution: 2.5–50 mmol/L. Concentration of zinc standard solution before detection: 1 mmol/L. Mix order: DCTA solution (5 mL) → zinc standard solution (5 mL). Concentration of Tris-HCl buffer solution: 10 mmol/L. pH of Tris-HCl buffer solution: 8.5. Concentration of added QD solution: 5 μmol/L. Concentration of APDC solution: 100 μmol/L. Concentration of cadmium standard solution: 2.5 mmol/L. Concentration of mixed zinc standard solution: 0.5 mmol/L. Concentration of DCTA in mixed zinc standard solution: 1.25–25 mmol/L. Addition order: Tris-HCl buffer solution (2 mL) → QD solution (0.4 mL) → APDC solution (0.52 mL) → cadmium standard solution (0.008 mL) → mixed zinc standard solution (0.04 mL) → Tris-HCl buffer solution (1.032 mL). Excitation wavelength: 460 nm. Observation time: 3 min. All data in this figure is mean of five measurements.</p> ">
Abstract
:1. Introduction
2. Experimental
2.1. Instruments and Reagents
2.2. Fluorescence Intensity Measurements
3. Results and Discussion
3.1. The Stability of the Fluorescence Intensity of the QD Solution
3.2. Optimization of the Concentration of APDC in the Detection Cuvette
3.3. Optimization of the pH of the Tris-HCl Buffer Solution
3.4. Fluorescence Quenching Caused by the Etching Effect of APDC in the CdTe/CdS QD Solution
3.5. Fluorescence Recovery Caused by Addition of Cd2+ to the APDC/CdTe/CdS QD Solution
3.6. Analytical Performance of the APDC/CdTe/CdS QD Solution
3.7. Interference Study
3.8. Sample Analysis
4. Conclusions
Author Contributions
Funding
Conflicts of Interest
References
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QD Sensor/Fluorescent Probe | Linear Range (μmol/L) | LOD (μmol/L) | Reference |
---|---|---|---|
Ag2S QD | 1–40 | 0.5460 | [33] |
competitive immunochromatographic strips/gold nanoparticles QD | 0.0022–0.0712 | 0.0016 | [34] |
4,5-bis (N, N-di (2- hydroxyethyl) iminomethyl) acridine fluorescent probe | 1–30 | 0.1300 | [36] |
6-mercaptonicotinic acid/L-Cys/gold nanoparticles fluorescent probe | 0.2–1.7 | 0.1000 | [37] |
CdTe/CdS QD | 0.0784–5.338 | 0.0235 | This work |
Ion | Number | Detected by the QD Solution (μg/L) a | Detected by AAS (μg/L) a | Relative Error (%) | Standard Deviation (SD) (μg/L) | Relative Standard Deviation (RSD) (%) |
---|---|---|---|---|---|---|
Cd2+ | Sample 1 | 28.75 | 28.17 | 2.01 | 0.56 | 1.94 |
Sample 2 | 14.39 | 14.85 | 3.10 | 0.41 | 2.87 | |
Sample 3 | 32.81 | 33.59 | 2.32 | 0.77 | 2.35 |
Ion | Number | Added (μg/L) | Detected by the QD Solution (μg/L) a. | Recovery (%) | Standard Deviation (SD) (μg/L) | Relative Standard Deviation (RSD) (%) |
---|---|---|---|---|---|---|
Cd2+ | Sample 4 | 40 | 39.10 | 97.75 | 0.62 | 1.77 |
Sample 5 | 80 | 78.43 | 98.04 | 2.08 | 2.65 | |
Sample 6 | 200 | 202.59 | 101.3 | 4.01 | 1.98 | |
Sample 7 | 400 | 391.73 | 97.93 | 9.44 | 2.41 |
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Yin, Y.; Yang, Q.; Liu, G. Ammonium Pyrrolidine Dithiocarbamate-Modified CdTe/CdS Quantum Dots as a Turn-on Fluorescent Sensor for Detection of Trace Cadmium Ions. Sensors 2020, 20, 312. https://doi.org/10.3390/s20010312
Yin Y, Yang Q, Liu G. Ammonium Pyrrolidine Dithiocarbamate-Modified CdTe/CdS Quantum Dots as a Turn-on Fluorescent Sensor for Detection of Trace Cadmium Ions. Sensors. 2020; 20(1):312. https://doi.org/10.3390/s20010312
Chicago/Turabian StyleYin, Yuan, Qingliang Yang, and Gang Liu. 2020. "Ammonium Pyrrolidine Dithiocarbamate-Modified CdTe/CdS Quantum Dots as a Turn-on Fluorescent Sensor for Detection of Trace Cadmium Ions" Sensors 20, no. 1: 312. https://doi.org/10.3390/s20010312