ConspectusGold nanoparticles (AuNPs) exhibit unique size- and shape-dependent properties not obtainable at the macroscale. Gold nanorods (AuNRs), with their morphology-dependent optical properties, ability to convert light to heat, and high surface-to-volume ratios, are of great interest for biosensing, medicine, and catalysis. While the gold core provides many fascinating properties, this Account focuses on AuNP soft surface coatings, which govern the interactions of nanoparticles with the local environments. Postmodification of AuNP surface chemistry can greatly alter NP colloidal stability, nano-bio interactions, and functionality. Polyelectrolyte coatings provide controllable surface-coating thickness and charge, which impact the composition of the acquired corona in biological settings. Covalent modification, in which covalently bound ligands replace the original capping layer, is often performed with thiols and disulfides due to their ability to replace native coatings. N-heterocyclic carbenes and looped peptides expand the possible functionalities of the ligand layer.The characterization of surface ligands bound to AuNPs, in terms of ligand density and dynamics, remains a challenge. Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool for understanding molecular structures and dynamics. Our recent NMR work on AuNPs demonstrated that NMR data were obtainable for ligands on NPs with diameters up to 25 nm for the first time. This was facilitated by the strong proton NMR signals of the trimethylammonium headgroup, which are present in a distinct regime from other ligand protons’ signals. Ligand density analyses showed that the smallest AuNPs (below 4 nm) had the largest ligand densities, yet spin–spin T2 measurements revealed that these smallest NPs also had the most mobile ligand headgroups. Molecular dynamics simulations were able to reconcile these seemingly contradictory results.While NMR spectroscopy provides ligand information averaged over many NPs, the ligand distribution on individual particles’ surfaces must also be probed to fully understand the surface coating. Taking advantage of improvements in electron energy loss spectroscopy (EELS) detectors employed with scanning transmission electron microscopy (STEM), a single-layer graphene substrate was used to calibrate the carbon K-edge EELS signal, allowing quantitative imaging of the carbon atom densities on AuNRs with sub-nanometer spatial resolution. In collaboration with others, we revealed that the mean value for surfactant-bilayer-coated AuNRs had 10–30% reduced ligand density at the ends of the rods compared to the sides, confirming prior indirect evidence for spatially distinct ligand densities.Recent work has found that surface ligands on nanoparticles can, somewhat surprisingly, enhance the selectivity and efficiency of the electrocatalytic reduction of CO2 by controlling access to the active site, tuning its electronic and chemical environment, or denying entry to impurities that poison the nanoparticle surface to facilitate reduction. Looking to the future, while NMR and EELS are powerful and complementary techniques for investigating surface coatings on AuNPs, the frontier of this field includes the development of methods to probe the surface ligands of individual NPs in a high-throughput manner, to monitor nano-bio interactions within complex matrices, and to study structure–property relationships of AuNPs in biological systems.
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N-Heterocyclic carbene-stabilized gold nanoparticles and luminescent quantum dots
N-heterocyclic carbenes (NHCs) have attracted tremendous attention over the past decade, as it is expected to form strong coordination to transition metal complexes and surfaces. Here, we investigate the interactions between colloidal
gold nanoparticles (AuNPs), or luminescent quantum dots (QDs) and a multidentate NHC-based polymer ligand. The ligand design relies on the nucleophilic addition reaction between several NHC anchoring groups, short polyethylene glycol (PEG) blocks, and a polymer chain. We find that such NHC-decorated ligands rapidly coordinate onto both sets of nanocrystals, which is attributed to the inherent σ-donating nature (soft Lewis base) of NHC groups combined with the soft Lewis acidic character of nanocrystal surfaces. We combine NMR spectroscopy, fluorescence spectroscopy, high-resolution transmission electron microscopy and dynamic light scattering to characterize the NHCstabilized nanocrystals and gain insights into the nature of the binding interactions. In particular, we find that the newly coated nanocrystals exhibit long-term colloidal stability over a broad range of conditions with no sign of
degradation or aggregation build up, while preserving their photophysical properties, for at least one year of storage.
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- Award ID(s):
- 2005079
- NSF-PAR ID:
- 10406489
- Editor(s):
- Osiński, Marek; Kanaras, Antonios G.
- Date Published:
- Journal Name:
- Colloidal Nanoparticles for Biomedical Applications XVII
- Volume:
- 11977
- Page Range / eLocation ID:
- 10
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Directing the assembly of nanoscale building blocks into programmable superstructures is of broad scientific and technological interest. Advances in nanocrystal self‐assembly at fluid interfaces are combined with digital light processing to demonstrate that how the extent and spatial region of superlattice structure transformation can be controlled. It is shown that the addition of a photoacid generator to the fluid subphase provides new experimental degrees of freedom to modulate the dynamic equilibrium of ligands bound to the colloidal nanocrystal surface. Within the photoexposed regions, the nanocrystal ligand coverage is reduced which impacts the interactions between proximate nanocrystals and drives the transformation from a sixfold to a fourfold symmetric superlattice. Structural analysis is presented from transmission electron microscopy and chemical analysis is presented from infrared spectroscopy to establish the relationship between superlattice structure and ligand coverage. Beyond new insights understanding of and control over deprotection of colloidal nanocrystals at fluid interfaces, the processing method described in this work presents new opportunities to create nanocrystal assemblies with spatially programmable structures.
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Colloidal nanocrystals consist of an inorganic crystalline core with organic ligands bound to the surface and naturally self-assemble into periodic arrays known as superlattices. This periodic structure makes superlattices promising for phononic crystal applications. To explore this potential, we use plane wave expansion methods to model the phonon band structure. We find that the nanoscale periodicity of these superlattices yield phononic band gaps with very high center frequencies on the order of 10 2 GHz. We also find that the large acoustic contrast between the hard nanocrystal cores and the soft ligand matrix lead to very large phononic band gap widths on the order of 10 1 GHz. We systematically vary nanocrystal core diameter, d , nanocrystal core elastic modulus, E NC core , interparticle distance ( i.e. ligand length), L , and ligand elastic modulus, E ligand , and report on the corresponding effects on the phonon band structure. Our modeling shows that the band gap center frequency increases as d and L are decreased, or as E NC core and E ligand are increased. The band gap width behaves non-monotonically with d , L , E NC core , and E ligand , and intercoupling of these variables can eliminate the band gap. Lastly, we observe multiple phononic band gaps in many superlattices and find a correlation between an increase in the number of band gaps and increases in d and E NC core . We find that increases in the property mismatch between phononic crystal components ( i.e. d / L and E NC core / E ligand ) flattens the phonon branches and are a key driver in increasing the number of phononic band gaps. Our predicted phononic band gap center frequencies and widths far exceed those in current experimental demonstrations of 3-dimensional phononic crystals. This suggests that colloidal nanocrystal superlattices are promising candidates for use in high frequency phononic crystal applications.more » « less
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Colloidal lead halide perovskite quantum dots (PQDs) are relatively new semiconductor nanocrystals with great potential for use in optoelectronic applications. They also present a set of new scientifically challenging fundamental problems to investigate and understand. One of them is to address the rather poor colloidal and structural stability of these materials under solution phase processing and/or transfer between solvents. In this contribution, we detail the synthesis of a new family of multi-coordinating, bromide-based polysalt ligands and test their ability to stabilize CsPbBr 3 nanocrystals in polar solutions. The ligands present multiple salt groups involving quaternary cations, namely ammonium and imidazolium as anchors for coordination onto PQD surfaces, along with several alkyl chains with varying chain length to promote solubilization in various conditions. The ligands provide a few key benefits including the ability to repair damaged surface sites, allow rapid ligand exchange and phase transfer, and preserve the crystalline structure and morphology of the nanocrystals. The polysalt-coated PQDs exhibit near unity PLQY and significantly enhanced colloidal stability in ethanol and methanol.more » « less
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The exceptional stability of N-heterocyclic carbene (NHC) monolayers on gold surfaces and nanoparticles (AuNPs) is enabling new and diverse applications from catalysis to biomedicine. Our understanding of NHC reactivity at surfaces; however, is quite nascent when compared to the long and rich history of NHC ligands in organometallic chemistry. In this work, well-established transmetalation reactions, previously developed for NHC transfer in homogeneous organometallic systems, are explored to determine how they can be used to create carbene functionalized gold surfaces. Two classes of NHCs, based on imidazole and benzimidazole scaffolds, were tested. The resulting AuNP surfaces were analyzed using X-ray photoelectron spectroscopy (XPS), laser desorption ionization mass spectrometry (LDI-MS), and surface-enhanced Raman spectroscopy (SERS). Reaction of either a Au( i ) or Ag( i ) isopropyl benzimidazole NHC complex with citrate-capped AuNPs yields, in both cases, a chemisorbed NHC that is bound through a Au adatom. Theoretical calculations additionally illustrate that binding through the Au adatom is favored by more than 10 kcal mol −1 , in good agreement with experiments. Surprisingly, reaction of Au( i ), Ag( i ), and Cu( i ) diisopropylphenyl imidazole NHCs do not follow the same pattern. The Cu complex undergoes transmetalation with very little deposition of Cu; whereas, unexpectedly, the Ag complex foregoes transmetalation and instead adducts to the AuNP with retention of the Ag–C bond. Theoretical calculations illustrate that the imidazole ligand affords significant dispersion interactions with the gold surface, which may stabilize binding through the Ag adatom motif, despite its less favorable bonding energies. Taken together these results suggest a unique ability to tune the reactivity by changing the carbene structure and raise critical questions about how established transmetalation reactions in organometallic chemistry can be applied to form NHC functionalized surfaces.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Conference Paper:
- https://doi.org/10.1117/12.2610485
