Gold Nanoclusters Prepared in the Presence of Adenosine Monophosphate and Citrate: Factorial-Based Synthesis Optimization and Sensing Properties
Abstract
:1. Introduction
2. Materials and Methods
2.1. Chemicals
2.2. General Synthesis Procedure
2.3. Order of Components Mixing
2.4. Factorial Design of AuNCs Synthesis
2.5. Sensitivity to Metal Ions
2.6. Characterization and Data Processing
3. Results
3.1. Order of Mixing
3.2. Factorial-Based Synthesis Design
3.3. Optimization of the Synthesis Conditions to Maximize the Quantum Yield
3.4. Optimization of the Synthesis Conditions to Maximize the Yellow Emission
3.5. Blue and Yellow AuNCs Prepared under the Optimal Conditions
- Sample A—cAu 0.2 mmol/L, rAMP 40, razide 0, rcitr 200, and rNa/H 0.5;
- Sample B—cAu 0.2 mmol/L, rAMP 5, razide 8.5, rcitr 275, and rNa/H 0.75.
4. Discussion
- If HAuCl4 was first mixed with citrate and then AMP and NaN3 were added, the absorption spectra were weaker in the 300–350 nm characteristic range, showing long-wave scattering (blue and pink curves in Figure 1a). The formation of larger gold species via the reduction of citrate in the absence of an efficient stabilizer (AMP) could explain that fact. Due to low absorbance at 365 nm, the normalized emission intensity was still comparable to other spectra (Figure 1b);
- If NaN3 was added to the mixture after AMP and citrate, the long-wave yellow emission was suppressed (blue and brown curves in Figure 1a). Hence, although the AuNCs formation in the AMP + HAuCl4 + citrate system was complete only within 2–3 h at 90 °C (taking days at room temperature [11,12]), its initial stage was fast, and the formed intermediate was not sensitive to NaN3 which did not impart yellow emission in that case;
- If citrate was the last component introduced prior to dilution and heating, the spectral properties of the product were independent of the order of AMP and NaN3 addition (red and green curves). Hence, the competing coordination of AMP and NaN3 with gold(III) before the reduction was fast, and the mixture came to equilibrium within 15 min after adding the components. On the other hand, our trials showed that the interaction of HAuCl4 with AMP alone was slower (yellow coloration due to the complex formation was developed within hours). Likely, the interaction of HAuCl4 with AMP was multistage: the initial coordination was relatively fast and could affect the AuNCs synthesis, whereas complete ligand exchange leading to the coloration was slower.
5. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Appendix A
Sample No. | cAu | rAMP | rcitr | rNa/H | razide |
---|---|---|---|---|---|
1 | 0 | 0 | 0 | 0 | 0 |
2 | 0 | 0 | 0 | 0 | 0 |
3 | 0 | 0 | 0 | 0 | 0 |
4 | 0 | 0 | 0 | 0 | −1 |
5 | 0 | 0 | 0 | 0 | −1 |
6 | 0 | 0 | 0 | 0 | −1 |
7 | −1 | −1 | −1 | −1 | −1 |
8 | −1 | −1 | −1 | −1 | 1 |
9 | −1 | −1 | −1 | 1 | −1 |
10 | −1 | −1 | −1 | 1 | 1 |
11 | −1 | −1 | 1 | −1 | −1 |
12 | −1 | −1 | 1 | −1 | 1 |
13 | −1 | −1 | 1 | 1 | −1 |
14 | −1 | −1 | 1 | 1 | 1 |
15 | −1 | 1 | −1 | −1 | −1 |
16 | −1 | 1 | −1 | −1 | 1 |
17 | −1 | 1 | −1 | 1 | −1 |
18 | −1 | 1 | −1 | 1 | 1 |
19 | −1 | 1 | 1 | −1 | −1 |
20 | −1 | 1 | 1 | −1 | 1 |
21 | −1 | 1 | 1 | 1 | −1 |
22 | −1 | 1 | 1 | 1 | 1 |
23 | 1 | −1 | −1 | −1 | −1 |
24 | 1 | −1 | −1 | −1 | 1 |
25 | 1 | −1 | −1 | 1 | −1 |
26 | 1 | −1 | −1 | 1 | 1 |
27 | 1 | −1 | 1 | −1 | −1 |
28 | 1 | −1 | 1 | −1 | 1 |
29 | 1 | −1 | 1 | 1 | −1 |
30 | 1 | −1 | 1 | 1 | 1 |
31 | 1 | 1 | −1 | −1 | −1 |
32 | 1 | 1 | −1 | −1 | 1 |
33 | 1 | 1 | −1 | 1 | −1 |
34 | 1 | 1 | −1 | 1 | 1 |
35 | 1 | 1 | 1 | −1 | −1 |
36 | 1 | 1 | 1 | −1 | 1 |
37 | 1 | 1 | 1 | 1 | −1 |
38 | 1 | 1 | 1 | 1 | 1 |
Sample No. | rAMP | rcitr | rNa/H | razide |
---|---|---|---|---|
75 | 0 | 0 | 0 | 0 |
76 | 0 | 0 | 0 | 0 |
77 | 0 | 0 | 0 | 0 |
78 | −1 | −1 | −1 | −1 |
79 | 1 | −1 | −1 | −1 |
80 | −1 | 1 | −1 | −1 |
81 | 1 | 1 | −1 | −1 |
82 | −1 | −1 | 1 | −1 |
83 | 1 | −1 | 1 | −1 |
84 | −1 | 1 | 1 | −1 |
85 | 1 | 1 | 1 | −1 |
86 | −1 | −1 | −1 | 1 |
87 | 1 | −1 | −1 | 1 |
88 | −1 | 1 | −1 | 1 |
89 | 1 | 1 | −1 | 1 |
90 | −1 | −1 | 1 | 1 |
91 | 1 | −1 | 1 | 1 |
92 | −1 | 1 | 1 | 1 |
93 | 1 | 1 | 1 | 1 |
Appendix B
Factor (Interaction) | SS | DF | F | P |
---|---|---|---|---|
cAu | 0.352 | 1 | 0.122 | 0.730 |
rAMP | 1.04 | 1 | 0.362 | 0.553 |
razide | 73.1 | 1 | 25.5 | 4.7∙10−5 |
rcitr | 0.071 | 1 | 0.025 | 0.876 |
rNa/H | 86.9 | 1 | 30.3 | 1.6∙10−5 |
cAu:rAMP | 0.003 | 1 | 0.001 | 0.974 |
cAu:razide | 0.077 | 1 | 0.027 | 0.872 |
cAu:rcitr | 0.073 | 1 | 0.025 | 0.875 |
cAu:rNa/H | 0.001 | 1 | 0.0004 | 0.985 |
rAMP:razide | 0.598 | 1 | 0.208 | 0.653 |
rAMP:rcitr | 0.343 | 1 | 0.119 | 0.733 |
rAMP:rNa/H | 0.869 | 1 | 0.302 | 0.588 |
razide:rcitr | 1.321 | 1 | 0.460 | 0.505 |
razide:rNa/H | 0.493 | 1 | 0.172 | 0.683 |
rcitr:rNa/H | 2.525 | 1 | 0.879 | 0.359 |
Residuals | 63.2 | 22 |
Factor (Interaction) | SS | DF | F | P |
---|---|---|---|---|
cAu | 0.001 | 1 | 5.45 | 0.035 |
rAMP | 0.057 | 1 | 257 | 2∙10−10 |
razide | 0.720 | 1 | 3233 | <10−15 |
rcitr | 0.001 | 1 | 3.50 | 0.082 |
rNa/H | 0.050 | 1 | 227 | 5∙10−10 |
cAu:rAMP | <0.001 | 1 | 0.602 | 0.450 |
cAu:razide | <0.001 | 1 | 0.051 | 0.824 |
cAu:rcitr | <0.001 | 1 | 0.003 | 0.956 |
cAu:rNa/H | <0.001 | 1 | 1.02 | 0.330 |
rAMP:razide | 0.051 | 1 | 230 | 4∙10−10 |
rAMP:rcitr | <0.001 | 1 | 0.262 | 0.617 |
rAMP:rNa/H | <0.001 | 1 | 1.10 | 0.312 |
razide:rcitr | 0.003 | 1 | 15.5 | 0.001 |
razide:rNa/H | 0.092 | 1 | 411 | 9∙10−12 |
rcitr:rNa/H | <0.001 | 1 | 1.56 | 0.232 |
Residuals | 0.003 | 14 |
Factor (Interaction) | SS | DF | F | P |
---|---|---|---|---|
rAMP | 2.93 | 1 | 267 | 2∙10−7 |
razide | 0.023 | 1 | 2.12 | 0.184 |
rcitr | 0.106 | 1 | 9.66 | 0.014 |
rNa/H | 0.653 | 1 | 59.6 | 6∙10−5 |
rAMP:razide | <0.001 | 1 | 0.026 | 0.875 |
rAMP:rcitr | 0.004 | 1 | 0.409 | 0.540 |
rAMP:rNa/H | 0.181 | 1 | 16.5 | 0.003 |
razide:rcitr | 0.017 | 1 | 1.55 | 0.248 |
razide:rNa/H | 0.003 | 1 | 0.268 | 0.619 |
rcitr:rNa/H | 0.001 | 1 | 0.081 | 0.784 |
Residuals | 0.088 | 8 |
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Karpushkin, E.; Mesnyankina, E.; Sergeyev, V. Gold Nanoclusters Prepared in the Presence of Adenosine Monophosphate and Citrate: Factorial-Based Synthesis Optimization and Sensing Properties. Analytica 2023, 4, 415-431. https://doi.org/10.3390/analytica4040030
Karpushkin E, Mesnyankina E, Sergeyev V. Gold Nanoclusters Prepared in the Presence of Adenosine Monophosphate and Citrate: Factorial-Based Synthesis Optimization and Sensing Properties. Analytica. 2023; 4(4):415-431. https://doi.org/10.3390/analytica4040030
Chicago/Turabian StyleKarpushkin, Evgeny, Ekaterina Mesnyankina, and Vladimir Sergeyev. 2023. "Gold Nanoclusters Prepared in the Presence of Adenosine Monophosphate and Citrate: Factorial-Based Synthesis Optimization and Sensing Properties" Analytica 4, no. 4: 415-431. https://doi.org/10.3390/analytica4040030