Aqueous suspension droplets of monodisperse latex or latex and gold nanoparticles mixtures assume spherical shape on superhydrophobic substrates. The drying sessile droplets serve as macroscopic templates for assembling microspheres into closed‐packed structures. Upon illumination, the supraparticles display discrete colored rings because of the periodic arrangement of latex particles in the surface layer. The physical origin of the colored patterns is explained in detail.
Agglomeration of nanoparticles during measurements in relevant biological and environmental media is a frequent problem in nanomaterial property characterization. The primary problem is typically that any changes to the size distribution can dramatically affect the potential nanotoxicity or other size-determined properties, such as the absorbance signal in a biosensor measurement. Herein we demonstrate analytical ultracentrifugation (AUC) as a powerful method for measuring two critical characteristics of nanoparticle (NP) agglomerates in situ in biological media: the NP agglomerate size distribution, and the localized surface plasmon resonance (LSPR) absorbance spectrum of precise sizes of gold NP agglomerates. To characterize the size distribution, we present a theoretical framework for calculating the hydrodynamic diameter distribution of NP agglomerates from their sedimentation coefficient distribution. We measure sedimentation rates for monomers, dimers, and trimers, as well as for larger agglomerates with up to 600 NPs. The AUC size distributions were found generally to be broader than the size distributions estimated from dynamic light scattering and diffusion-limited colloidal aggregation theory, an alternative bulk measurement method that relies on several assumptions. In addition, the measured sedimentation coefficients can be used in nanotoxicity studies to predict how quickly the agglomerates sediment out of solution under normal gravitational forces, such as in the environment. We also calculate the absorbance spectra for monomer, dimer, trimer, and larger gold NP agglomerates up to 600 NPs, to enable a better understanding of LSPR biosensors. Finally, we validate a new method that uses these spectra to deconvolute the net absorbance spectrum of an unknown bulk sample and approximate the proportions of monomers, dimers, and trimers in a polydisperse sample of small agglomerates, so that every sample does not need to be measured by AUC. These results demonstrate the potential utility of AUC to characterize NP agglomeration and sedimentation for nanotoxicity and biosensor studies, as well as to characterize NP agglomerate size and absorbance to improve LSPR and surface-enhanced Raman spectroscopy based biosensors.
The structure and density of the bound interfacial surfactant layer and associated hydration shell were investigated using analytical ultracentrifugation for length and chirality purified (6,5) single-wall carbon nanotubes (SWCNTs) in three different bile salt surfactant solutions. The differences in the chemical structures of the surfactants significantly affect the size and density of the bound surfactant layers. As probed by exchange of a common parent nanotube population into sodium deoxycholate, sodium cholate, or sodium taurodeoxycholate solutions, the anhydrous density of the nanotubes was least for the sodium taurodeoxycholate surfactant, and the absolute sedimentation velocities greatest for the sodium cholate and sodium taurodeoxycholate surfactants. These results suggest that the thickest interfacial layer is formed by the deoxycholate, and that the taurodeoxycholate packs more densely than either sodium cholate or deoxycholate. These structural differences correlate well to an observed 25% increase in fluorescence intensity relative to the cholate surfactant for deoxycholate and taurodeoxycholate dispersed SWCNTs displaying equivalent absorbance spectra. Separate sedimentation velocity experiments including the density modifying agent iodixanol were used to establish the buoyant density of the (6,5) SWCNT in each of the bile salt surfactants; from the difference in the buoyant and anhydrous densities, the largest hydrated diameter is observed for sodium deoxycholate. Understanding the effects of dispersant choice and the methodology for measurement of the interfacial density and hydrated diameter is critical for rationally advancing separation strategies and applications of nanotubes.
We demonstrate how droplet templates dispensed on superhydrophobic substrates can be used to fabricate both shape-anisotropic ("doughnut") and composition-anisotropic ("patchy magnetic") supraparticles. The macroscopic shape of the closely-packed particle assemblies is guided by the droplet meniscus. Aqueous droplets of monodisperse microsphere suspensions dispensed on the substrates initially acquire near-spherical shape due to a high contact angle. During the solvent evaporation, however, silica suspension droplets undergo shape transitions (concaving) guiding the structure of the final assemblies into doughnut supraparticles. Composition anisotropy is achieved by drying a droplet containing a mixed suspension of latex and magnetic nanoparticles, while exposing it to magnetic field gradients. Depending on the pattern of the magnetic fields, the magnetic nanoparticles segregate into single, bilateral, or trilateral, patched spherical supraparticles. The physical effects leading to the development of anisotropy are discussed. Unlike the conventional wet self-assembly (WSA) methods where the final structures need to be extracted from the liquid environment, this efficient one-step procedure produces ready to use "dry" supraparticles.
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