Acetone-Water Interactions in Crystalline and Amorphous Ice Environments.

We present research that systematically examines acetone interacting with various D2O ices of terrestrial and astrophysical interest using time-resolved, in situ reflection absorption infrared spectroscopy (RAIRS). We examine acetone deposited on top of different D2O ice films: high-density, nonporous amorphous (np-ASW), and crystalline (CI) films as well as porous amorphous (p-ASW) with various pore morphologies. Analysis of RAIR spectra changes after acetone exposure, and we find that more hydrogen bonding occurs between acetone and p-ASW ices as compared to acetone and np-ASW or CI ices. Hydrogen bonding quantification occurred by two independent RAIR spectral changes: a greater relative intensity of the 1703 cm-1 feature at low acetone coverage as part of a 14 cm-1 shift in the C═O region and an ∼30% integrated dangling bond area reduction after acetone exposure. Interestingly, when changing the water structure to be more porous (deposited at 70° compared to 30°), there is a further reduction in the amount of hydrogen bonding that occurs. This suggests that there is a lack of access to surface sites with dangling bonds in the pores as initial layers of acetone block the pores and acetone is unable to diffuse within the structure at low temperatures. In general, these results offer a clearer picture of the mechanisms that can occur when small organic hydrocarbons interact with various icy interfaces; a quantitative understanding of these interactions is essential for the accurate modeling of many astrophysical processes occurring on the surface of icy dust particles.

Differential Condensation of Methane Isotopologues Leading to Isotopic Enrichment under Non-equilibrium Gas-Surface Collision Conditions.

We examine the initial differential sticking probability of CH4 and CD4 on CH4 and CD4 ices under nonequilibrium flow conditions using a combination of experimental methods and numerical simulations. The experimental methods include time-resolved in situ reflection-absorption infrared spectroscopy (RAIRS) for monitoring on-surface gaseous condensation and complementary King and Wells mass spectrometry techniques for monitoring sticking probabilities that provide confirmatory results via a second independent measurement method. Seeded supersonic beams are employed so that the entrained CH4 and CD4 have the same incident velocity but different kinetic energies and momenta. We found that as the incident velocity of CH4 and CD4 increases, the sticking probabilities for both molecules on a CH4 condensed film decrease systematically, but that preferential sticking and condensation occur for CD4. These observations differ when condensed CD4 is used as the target interface, indicating that the film's phonon and rovibrational densities of states, and collisional energy transfer cross sections, have a role in differential energy accommodation between isotopically substituted incident species. Lastly, we employed a mixed incident supersonic beam composed of both CH4 and CD4 in a 3:1 ratio and measured the condensate composition as well as the sticking probability. When doing so, we see the same effect in the condensed mixed film, supporting an isotopic enrichment of the heavier isotope. We propose that enhanced multi-phonon interactions and inelastic cross sections between the incident CD4 projectile and the CH4 film allow for more efficacious gas-surface energy transfer. VENUS code MD simulations show the same sticking probability differences between isotopologues as observed in the gas-surface scattering experiments. Ongoing analyses of these trajectories will provide additional insights into energy and momentum transfer between the incident species and the interface. These results offer a new route for isotope enrichment via preferential condensation of heavier isotopes and isotopologues during gas-surface collisions under specifically selected substrate, gas-mixture, and incident velocity conditions. They also yield valuable insights into gaseous condensation under non-equilibrium conditions such as occur in aircraft flight in low-temperature environments. Moreover, these results can help to explain the increased abundance of deuterium in solar system planets and can be incorporated into astrophysical models of interstellar icy dust grain surface processes.

Rapid nondestructive measurement of bacterial cultures with 3D interferometric imaging.

The agar culture plate has played a crucial role in bacteriology since the origins of the discipline and is a staple bioanalytical method for efforts ranging from research to standard clinical diagnostic tests. However, plating, inoculating, and waiting for microbes to develop colonies that are visible is time-consuming. In this work, we demonstrate white-light interferometry (WLI) as a practical tool for accelerated and improved measurement of bacterial cultures. High resolution WLI surface profile imaging was used for nondestructive characterization and counting of bacterial colonies on agar before they became visible to the naked eye. The three-dimensional (3D) morphology of Gram-negative (Pseudomonas fluorescens) and Gram-positive (Bacillus thuringiensis) bacterial species were monitored with WLI over time by collecting surface profiles of colonies on agar plates with high vertical resolution (3-5 nanometers) and large field of view (3-5 mm). This unique combination of sensitive vertical resolution and large field of view uniquely provided by WLI enables measurement of colony morphologies and nondestructive monitoring of hundreds of microcolonies. Individual bacteria were imaged within the first few hours after plating and colonies were accurately counted with results comparing favorably to counts made by traditional methods that require much longer wait times. Nondestructive imaging was used to track single cells multiplying into small colonies and the volume changes over time in these colonies were used to measure their growth rates. Based on the results herein, bioimaging with WLI was demonstrated as a novel rapid bacterial culture assay with several advantageous capabilities. Fast nondestructive counting of colony-forming units in a culture and simultaneous measurement of bacterial growth rates and colony morphology with this method may be beneficial in research and clinical applications where current methods are either too slow or are destructive.

Monitoring bacterial biofilms with a microfluidic flow chip designed for imaging with white-light interferometry.

There is a need for imaging and sensing instrumentation that can monitor transitions in a biofilm structure in order to better understand biofilm development and emergent properties such as anti-microbial resistance. Herein, we describe the design, manufacture, and use of a microfluidic flow cell to visualize the surface structure of bacterial biofilms with white-light interferometry (WLI). The novel imaging chip enabled the use of this non-disruptive imaging method for the capture of high resolution three-dimensional profile images of biofilm growth over time. The fine axial resolution (3 nm) and the wide field of view (>1 mm by 1 mm) enabled the detection of biofilm formation as early as 3 h after inoculation of the flow cell with a live bacterial culture (Pseudomonas fluorescens). WLI imaging facilitated the monitoring of the early stages of biofilm development and subtle variations in the structure of mature biofilms. Minimally-invasive imaging enabled the monitoring of biofilm structure with surface metrology metrics (e.g., surface roughness). The system was used to observe a transition in the biofilm structure that occurred in response to exposure to a common antiseptic. In the future, WLI and the biofilm imaging cell described herein may be used to test the effectiveness of biofilm-specific therapies to combat common diseases associated with biofilm formation such as cystic fibrosis and periodontitis.