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Cloudwater and below-cloud atmospheric particle samples were collected onboard a research aircraft during the Southern Oxidant and Aerosol Study (SOAS) over a forested region of Alabama in June 2013. The organic molecular composition of the samples was studied to gain insights into the aqueous-phase processing of organic compounds within cloud droplets. High resolution mass spectrometry (HRMS) with nanospray desorption electrospray ionization (nano-DESI) and direct infusion electrospray ionization (ESI) were utilized to compare the organic composition of the particle and cloudwater samples, respectively. Isoprene and monoterpene-derived organosulfates and oligomers were identified in both the particles and cloudwater, showing the significant influence of biogenic volatile organic compound oxidation above the forested region. While the average O:C ratios of the organic compounds were similar between the atmospheric particle and cloudwater samples, the chemical composition of these samples was quite different. Specifically, hydrolysis of organosulfates and formation of nitrogen-containing compounds were observed for the cloudwater when compared to the atmospheric particle samples, demonstrating that cloud processing changes the composition of organic aerosol.

Single-particle longitudinal motion and pairwise lateral motion was investigated while the particles were excited by an oscillating electric field directed normally to an electrode proximate to the particles. The electrode was polarized over a range of potential insufficient to drive electrochemical reactions, a range called the "ideally polarizable region". The particles' motion was qualitatively dependent on the choice of electrolyte despite the absence of electrochemical reactions. As when electrochemical reactions were not explicitly excluded, the phase angle θ between particle height and electric field correlated with the particles' separation or aggregation during excitation. A simple harmonic oscillator model of the particles' response, including colloidal and hydrodynamic forces and including the Basset force not previously cited in this context, showed how θ can increase from 0° at low frequencies, cross 90° at ∼100 Hz, and then increase to 180° as frequency was increased. The model captured the essence of experimental observations discussed here and in earlier works. This is the first a priori prediction of θ for this problem.

The two-particle interaction between 3.1-μm-diameter polystyrene latex particles at a decane-water interface was measured with time-shared optical tweezers. The water subphase contained either 0.103 mM RbCl or 0.0342 mM MgCl2, which have hydrated cations of different size but identical anions. The choice of both the anion and the concentrations makes a comparison with published data on NaCl possible and also isolates the effect of the nature of the cation on the electrostatic interaction. The measured magnitude of the dipolar force and the relative changes as a function of electrolyte were in quantitative agreement with predictions from a recently published model that uses the Langevin-Poisson-Boltzmann equation including steric effects and the polarization saturation of the medium to predict the dipolar interaction (Frydel, D.; Oettel, M. Phys. Chem. Chem. Phys. 2011, 13, 4109-4118). These results support the hypothesis that a condensed layer of counterions contributes to the electrostatic interaction between colloidal particles at an oil-water interface. Although it has been suggested that the electrostatic interactions between particles at liquid interfaces could serve as a sensitive probe of the structural details of the electric double layer, both the model predictions and experimental measurements showed a maximum change of only ~25% in the magnitude of the interaction with a change in electrolyte under the conditions tested. The ability to resolve this small change was confounded by the heterogeneous nature of the interaction. Thus, despite the apparent importance of the choice of electrolyte, the subtlety of competing effects makes it unlikely that colloidal force measurements could be used to probe the fine structure of the electric double layer.

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Janus particles have anisotropy in surface chemistry or composition that will effect dynamics and interactions with neighboring surfaces. One specific type of Janus particle is that consisting of a native micrometer-scale particle with a cap of gold, platinum, or another metal deposited with a typical thicknesses of ∼10 nm. A key characteristic of metal-capped Janus particles prepared with glancing angle deposition is the cap thickness. The nominal thickness is usually assumed to be uniform across the cap for modeling or interpretation of data, but the vapor deposition fabrication process likely does not produce such a cap because of the particle's curvature. These nonuniformities in the cap thickness may have a profound impact on Janus particle dynamics at equilibrium and in response to external fields. Herein, we summarize an experimental technique that utilizes focused ion beam slicing, image analysis, and results for the direct and local measure of cap thickness for 5 μm polystyrene spheres with a gold cap of nominal thicknesses of 10 or 20 nm. We found the cap varied in thickness continuously along the perimeter of the particle and also that the deposition rate, varying between 0.5 and 2.0 Å/s, did not significantly alter the way in which the thickness varied. These data support the hypothesis that cap thickness of a Janus sphere will vary across the gold surface contour, while demonstrating a feasible route for direct measurement of Janus particle cap thickness.

The liquid phase processing including dispersion, purification, and assembly of boron nitride nanotubes (BNNTs) is important for effectively translating unique properties of BNNTs into assembled solid materials, such as films and fibers. Short single-stranded DNA (ssDNA) has been the biopolymer of choice to achieve efficient sorting and assembly of carbon nanotubes, which are structural analogues to BNNTs. Here, we demonstrated a highly efficient aqueous dispersion of BNNTs using (GT)20 ssDNA and the subsequent removal of non-nanotube impurities from dispersions of as-synthesized BNNT material by a membrane filtration approach. The surface coating of BNNTs by DNA creates uniform dispersions at a nanotube concentration of as high as ≈11.5 mass %, leading to the formation of solid aligned films after solvent evaporation without applied shear, therefore demonstrating the first example of BNNT films produced by spontaneous alignment of nanotubes. Our findings provide important insights for producing macroscopic assemblies of aligned BNNT films for potential applications in thermal interface material and electronic and optoelectronic devices.

This article describes the simulated Brownian motion of a sphere comprising hemispheres of unequal zeta potential (i.e., "Janus" particle) very near a wall. The simulation tool was developed and used to assist in the methodology development for applying Total Internal Reflection Microscopy (TIRM) to anisotropic particles. Simulations of the trajectory of a Janus sphere with cap density matching that of the base particle very near a boundary were used to construct 3D potential energy landscapes that were subsequently used to infer particle and solution properties, as would be done in a TIRM measurement. Results showed that the potential energy landscape of a Janus sphere has a transition region at the location of the boundary between the two Janus halves, which depended on the relative zeta potential magnitude. The potential energy landscape was fit to accurately obtain the zeta potential of each hemisphere, particle size, minimum potential energy position and electrolyte concentration, or Debye length. We also determined the appropriate orientation bin size and regimes over which the potential energy landscape should be fit to obtain system properties. Our simulations showed that an experiment may require more than 10 observations to obtain a suitable potential energy landscape as a consequence of the multivariable nature of observations for an anisotropic particle. These results illustrate important considerations for conducting TIRM for anisotropic particles.