New Evidence of the Bidentate Binding Mode in 3-MBA Protected Gold Clusters: Analysis of Aqueous 13–18 kDa Gold-Thiolate Clusters by HPLC-ESI-MS Reveals Special Compositions Aun(3-MBA)p, (n = 48–67, p = 26–30)
Abstract
:1. Introduction
2. Materials and Methods
2.1. Synthesis
2.2. 3-MBA/Au System Characterization
2.2.1. Coupled Chromatography—ESI-MS
2.2.2. HP-LC–ESI-MS Sample Preparation
3. Results
4. Discussion
4.1. General Remarks
4.2. Contrasting 3-MBA (or Meta-MBA) and 4-MBA (Aka Para-MBA)
- There has been no total-structure determination of any 3-MBA protected gold clusters.
- There has been no adequately resolved ESI-MS identification of any of these: no composition-determination by any standard analytical method.
- Electron microscopy (or diffraction) provides the gold structure and atom count, in both (2) reported cases. (Ligands/S-atoms are not located by this method). Models are then constructed, which include the ligands, and these are tested (refined) by DFT computations.
- The compositions arrived at by these procedures, (68, 32) and (144, ~40), are respectively distinctly and strikingly different from those determined previously for aliphatic ligands, i.e., (67, 35) and (144, 60), or from the more directly relevant water-soluble aromatic pMBA ligand (146, 57). [Figure 6 presents these compositions in a graphical format.]
- In the carbonyl (C=O) stretching region, the vibrational FTIR spectra show “distinct peak[s] around 1730 cm−1, observable only in 3-MBA-passivated clusters, and interpreted as the signal of the O=C−OH···Au interaction.” [4].
- Molecular dynamic (MD) simulations were based on structure models for each cluster. “Visual inspection of MD trajectories revealed several weak interactions in the ligand layer and at the ligand−gold interface, such as formation of inter-ligand hydrogen bonds, inter-ligand π stacking (aromatic contacts), π−Au interaction where the aromatic ring lies “flat” on the gold core, and hydrogen bonding-like O=C−OH···Au interaction when the hydroxyl group is rotated toward the gold core.” “We thus assigned the highest frequency observed for both Au144(3-MBA)∼40 and Au68(3-MBA)32 to the O=C−OH···Au interaction visualized … This interaction at the ligand−metal interface has not been reported before for any thiolate protected gold nanocluster.” [4].
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Black, D.M.; Hoque, M.M.; Plascencia-Villa, G.; Whetten, R.L. New Evidence of the Bidentate Binding Mode in 3-MBA Protected Gold Clusters: Analysis of Aqueous 13–18 kDa Gold-Thiolate Clusters by HPLC-ESI-MS Reveals Special Compositions Aun(3-MBA)p, (n = 48–67, p = 26–30). Nanomaterials 2019, 9, 1303. https://doi.org/10.3390/nano9091303
Black DM, Hoque MM, Plascencia-Villa G, Whetten RL. New Evidence of the Bidentate Binding Mode in 3-MBA Protected Gold Clusters: Analysis of Aqueous 13–18 kDa Gold-Thiolate Clusters by HPLC-ESI-MS Reveals Special Compositions Aun(3-MBA)p, (n = 48–67, p = 26–30). Nanomaterials. 2019; 9(9):1303. https://doi.org/10.3390/nano9091303
Chicago/Turabian StyleBlack, David M., M. Mozammel Hoque, Germán Plascencia-Villa, and Robert L. Whetten. 2019. "New Evidence of the Bidentate Binding Mode in 3-MBA Protected Gold Clusters: Analysis of Aqueous 13–18 kDa Gold-Thiolate Clusters by HPLC-ESI-MS Reveals Special Compositions Aun(3-MBA)p, (n = 48–67, p = 26–30)" Nanomaterials 9, no. 9: 1303. https://doi.org/10.3390/nano9091303