Increased Cytotoxicity of Bimetallic Ultrasmall Silver–Platinum Nanoparticles (2 nm) on Cells and Bacteria in Comparison to Silver Nanoparticles of the Same Size
Abstract
:1. Introduction
2. Materials and Methods
2.1. Chemicals and Reagents
2.2. Electron Microscopy
2.3. X-ray Powder Diffraction (XRD)
2.4. Small-Angle X-ray Scattering (SAXS)
2.5. NMR Spectroscopy
2.6. DOSY-NMR Spectroscopy
2.7. X-ray Photoelectron Spectroscopy (XPS)
2.8. Elemental Analysis (AAS, ICP-MS)
2.9. Differential Centrifugal Sedimentation (DCS)
2.10. UV-Vis Spectroscopy
2.11. Fluorescence Spectroscopy
2.12. Synthesis of Glutathione-Coated Nanoparticles
2.13. Fluorescent Labeling of GSH-Coated Nanoparticles
2.14. Uptake of M-AF647 Nanoparticles by HeLa Cells
2.15. MTT Tests of M-GSH Nanoparticles with HeLa Cells
2.16. Antibacterial Tests of M-GSH Nanoparticles with Staphylococcus xylosus and Escherichia coli
3. Results
4. Discussion
5. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Au | Ag | Ag50Pt50 | Pt | |
---|---|---|---|---|
GSH-terminated nanoparticles used for the synthesis | 15 mg Au, 0.31 µmol nanoparticles | 15 mg Ag, 0.57 µmol nanoparticles | 6.47 mg Ag, 11.7 mg Pt, 0.48 µmol nanoparticles | 18.8 mg Pt, 0.35 µmol nanoparticles |
round-bottomed flask | 250 mL | 500 mL | 250 mL | 250 mL |
H2O | 18 mL | 36 mL | 20 mL | 24 mL |
methanol | 54 mL | 108 mL | 60 mL | 72 mL |
ISA | 184 mg, 676 µmol | 394 mg, 1.45 mmol | 221 mg, 812 µmol | 357 mg, 1.31 mmol |
K2CO3 | 94 mg, 676 µmol | 201 mg, 1.45 mmol | 113 mg, 812 µmol | 183 mg, 1.31 mmol |
5 mM CuSO4 solution | 1.04 mL, 5.2 µmol | 2.52 mL, 12.6 µmol | 3.67 mL, 18.4 µmol | 3.91 mL, 19.6 µmol |
1 M NaOH solution | 1 mL | 2 mL | 2 mL | 4 mL |
Reaction time | 72 h | 48 h | 48 h | 72 h |
Au | Ag | Ag50Pt50 | Pt | |
---|---|---|---|---|
N3-terminated nanoparticles used for the synthesis | 3 mg Au, 62 nmol nanoparticles | 2.54 mg Ag, 96 nmol nanoparticles | 1.85 mg Pt, 0.61 mg Ag, 61 nmol nanoparticles | 3.7 mg Pt, 68 nmol nanoparticles |
11.2 mM AF647-alkyne solution | 100 µL, 1.12 µmol, 1 mg | 155 µL, 1.73 µmol, 1.54 mg | 100 µL, 1.12 µmol, 1 mg | 61 µL, 0.68 µmol, 0.61 mg |
Cu-THPTA solution | 583 µL | 853 µL | 459 µL | 1.5 mL |
10 mM sodium ascorbate solution | 301 µL, 3.6 µmol, 0.6 mg | 246 µL, 2.46 µmol, 0.49 mg | 164 µL, 1.6 µmol, 0.33 mg | 535 µL, 5.4 µmol, 1.06 mg |
Reaction time | 17 h | 6 h | 17 h | 17 h |
Ag | Ag70Pt30 | Ag50Pt50 | Ag20Pt80 | Pt | Au | |
---|---|---|---|---|---|---|
particle core volume/nm3 | 4.19 * | 4.19 * | 4.19 * | 4.19 * | 4.19 * | 4.19 * |
particle core weight/g·1023 | 4.39 * | 5.54 * | 6.69 * | 7.84 * | 8.98 * | 8.09 * |
particle density/g cm−3 | 10.49 | 13.78 ** | 15.97 ** | 19.26 ** | 21.45 | 19.32 |
particle core surface area/nm2 | 12.57 * | 12.57 * | 12.57 * | 12.57 * | 12.57 * | 12.57 * |
hydrodynamic diameter (DCS)/nm | 1.7 ± 0.5 *** | 1.5 ± 0.3 | 1.6 ± 0.3 *** | 1.6 ± 0.4 | 1.6 ± 0.4 *** | 1.5 ± 0.3 *** |
diffusion coefficient (1H-DOSY)/10−10 m2 s−1 | 1.47 *** | 1.53 | 1.60 *** | 1.69 | 1.56 *** | 1.28 *** |
hydrodynamic diameter (1H-DOSY)/nm | 3.32 *** | 3.19 | 3.05 *** | 2.88 | 3.14 *** | 3.81 *** |
particle core diameter (HRTEM)/nm | 2.2 ± 0.5 *** | 1.9 ± 0.6 | 1.8 ± 0.4 *** | 1.8 ± 0.3 | 2.0 ± 0.4 *** | 2.0 ± 0.4 *** |
particle core diameter (SAXS)/nm | 1.0 ± 0.1 *** | 1.0 ± 0.1 | 1.6 ± 0.1 *** | 1.0 ± 0.1 | 0.9 ± 0.1 *** | 0.8 ± 0.2 |
crystallinity by TEM | crystalline *** | amorphous | amorphous *** | crystalline | crystalline *** | crystalline *** |
oxidation state of metals by XPS | Ag+ *** | Ag+, Pt, Pt2+ | Ag+, Pt, Pt2+ *** | Ag+, Pt, Pt2+ | Pt, Pt2+ *** | Au *** |
normalized molar ratio metal(M):sulfur(S) by ICP-MS | 1.00 (Ag):1.28 (S) *** | 0.71 (Ag):0.29 (Pt):0.65 (S) | 0.59 (Ag):0.41 (Pt):0.68 (S) *** | 0.16 (Ag):0.84 (Pt):1.35 (S) | 1.00 (Pt):0.73 (S) *** | 1.00 (Au):0.82 (S) *** |
overall nominal composition of one nanoparticle | Ag245GSH315 *** | Ag184Pt74GSH170 | Ag156Pt110GSH180 *** | Ag43Pt230GSH370 | Pt277GSH206 *** | Au247GSH203 *** |
GSH molecular footprint/nm2 | 0.040 *** | 0.074 | 0.070 *** | 0.034 | 0.062 *** | 0.062 *** |
number of conjugated AlexaFluor-647 molecules on each M-AF647 nanoparticle by AAS and UV-VIS | 13 | - | 8 | - | 6 | 12 |
c(Metal)/in µg mL−1 | Au | Ag | Ag70Pt30 | Ag50Pt50 | Ag/Pt (50:50) | Ag20Pt80 | Pt |
---|---|---|---|---|---|---|---|
0 | 100 ± 6 | 100 ± 5 (Ag: 0) | 100 ± 4 (Ag: 0) | 100 ± 9 (Ag: 0) | 100 ± 4 (Ag: 0) | 100 ± 2 (Ag: 0) | 100 ± 10 |
2.5 | 93 ± 6 | 92 ± 6 (Ag: 2.5) | 105 ± 2 (Ag: 1) | 107 ± 2 (Ag: 0.9) | 99 ± 7 (Ag: 0.9) | 98 ± 4 (Ag: 0) | 100 ± 3 |
5 | 99 ± 4 | 88 ± 7 (Ag: 5) | 110 ± 1 (Ag: 2.8) | 114 ± 4 (Ag: 1.8) | 100 ± 6 (Ag: 1.8) | 113 ± 5 (Ag: 0.6) | 97 ± 8 |
10 | 105 ± 5 | 79 ± 6 (Ag: 10) | 95 ± 4 (Ag: 5.6) | 99 ± 4 (Ag: 3.6) | 71 ± 12 (Ag: 3.6) | 99 ± 10 (Ag: 1) | 90 ± 5 |
15 | 93 ± 4 | 77 ± 5 (Ag: 15) | 90 ± 5 (Ag: 8.5) | 94 ± 5 (Ag: 5) | 62 ± 12 (Ag: 5) | 99 ± 4 (Ag: 1.8) | 84 ± 5 |
25 | 102 ± 6 | 91 ± 9 (Ag: 25) | 84 ± 6 (Ag: 14) | 97 ± 5 (Ag: 8.9) | 60 ± 8 (Ag: 8.9) | 105 ± 6 (Ag: 3) | 91 ± 4 |
50 | 93 ± 11 | 89 ± 10 (Ag: 50) | 26 ± 10 (Ag: 28) | 47 ± 6 (Ag: 18) | 54 ± 7 (Ag: 18) | 100 ± 4 (Ag: 6) | 90 ± 8 |
75 | 91 ± 6 | 78 ± 4 (Ag: 75) | 15 ± 10 (Ag: 42) | 13 ± 3 (Ag: 27) | 46 ± 14 (Ag: 27) | 85 ± 6 (Ag: 9) | 85 ± 3 |
100 | 97 ± 4 | 76 ± 5 (Ag: 100) | 11 ± 5 (Ag: 56) | 8 ± 4 (Ag: 36) | 44 ± 14 (Ag: 36) | 69 ± 3 (Ag: 12) | 87 ± 7 |
Sample | E. coli (Gram-Negative) | S. xylosus (Gram-Positive) |
---|---|---|
AgNO3 | 6–10 (6–10) | 15–25 (15–25) |
Ag | >100 (>100) | >100 (>100) |
Au | >100 (−) | >100 (−) |
Pt | >100 (−) | >100 (−) |
Ag50Pt50 | 11–15 (4–5.4) | 1–5 (0.4–1.8) |
Ag/Pt (50:50) | 76–100 (27–36) | >100 (>36) |
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Wolff, N.; Białas, N.; Loza, K.; Heggen, M.; Schaller, T.; Niemeyer, F.; Weidenthaler, C.; Beuck, C.; Bayer, P.; Prymak, O.; et al. Increased Cytotoxicity of Bimetallic Ultrasmall Silver–Platinum Nanoparticles (2 nm) on Cells and Bacteria in Comparison to Silver Nanoparticles of the Same Size. Materials 2024, 17, 3702. https://doi.org/10.3390/ma17153702
Wolff N, Białas N, Loza K, Heggen M, Schaller T, Niemeyer F, Weidenthaler C, Beuck C, Bayer P, Prymak O, et al. Increased Cytotoxicity of Bimetallic Ultrasmall Silver–Platinum Nanoparticles (2 nm) on Cells and Bacteria in Comparison to Silver Nanoparticles of the Same Size. Materials. 2024; 17(15):3702. https://doi.org/10.3390/ma17153702
Chicago/Turabian StyleWolff, Natalie, Nataniel Białas, Kateryna Loza, Marc Heggen, Torsten Schaller, Felix Niemeyer, Claudia Weidenthaler, Christine Beuck, Peter Bayer, Oleg Prymak, and et al. 2024. "Increased Cytotoxicity of Bimetallic Ultrasmall Silver–Platinum Nanoparticles (2 nm) on Cells and Bacteria in Comparison to Silver Nanoparticles of the Same Size" Materials 17, no. 15: 3702. https://doi.org/10.3390/ma17153702