an-inverse-analysis-approach-to-characterization-chemical-transport

An Inverse Analysis Approach to the Characterization of Chemical Transport in Paints

The ability to directly characterize chemical transport and interactions that occur within a material (i.e., subsurface dynamics) is a vital component in ...

OptiMetrics, Inc., a DCS Company

We report diffusion in the tunneling spectra of isolated, ligand-stabilized undecagold (Au11) clusters immobilized by attachment to alpha,omega-alkanedithiolate tethers inserted into alkanethiolate self-assembled monolayers. We use scanning tunneling microscopy and spectroscopy at cryogenic (UHV, 4 K) conditions to measure these clusters' conductance with complete control of their chemical and physical environment; additionally, thermal broadening of their electronic states as well as their mobility is minimized. At low temperature, the Au11 clusters demonstrate Coulomb blockade behavior, with zero-conductance gaps resulting from quantum size effects. Surprisingly, chemically identical and even single particles produced different families of tunneling spectra, comparable to previous results for heterogeneous distributions of particles. We hypothesize that, while these particles are chemically attached to the surface of the SAM for measurement, these assemblies may still be sufficiently dynamic to affect their transport properties significantly.

Spectral diffusion in the tunneling spectra of ligand-stabilized undecagold clusters.

The development of DNA-based biosensors requires a deep understanding of how DNA molecules adsorb and organize on solid state surfaces as well as the electronic properties of individual and aggregates of DNA molecules. Using scanning tunneling microscopy (STM) and atomic force microscopy (AFM), we have successfully characterized an attractive force driven molecular void formation for DNA chemically adsorbed on Au(111) as a function of strand length and deposition conditions. Here we report the observation of these void structures formed on the Au(111) surface by adsorption of both 45 and 90 base pair long, thiolated double-stranded DNA. We found that the average void diameter decreases when increasing the number of base pairs exposed to the surface. The critical determinant in the molecular void formation is the total charge delivered to the surface via the adsorption of the DNA strands and the related counterions, which can ultimately be quantified by the number of base pairs in each adsorbed DNA molecule. Complementary measurements involving STM and AFM suggest that an intact Au(111) surface area is preserved inside the void and is surrounded by a submonolayer of DNA molecules adsorbed on the surface. The discussion of the possible mechanisms for the void formation implies an effective attraction between the DNA molecules.

Molecular voids formed from effective attraction in submonolayer DNA deposited on Au(111).

Low temperature scanning tunneling microscopy and spectroscopy have been used to resolve modifications to the Ag(111) surface electronic structure due to the weak adsorption of the nucleobase adenine. Differential conductance spectroscopy recorded at 15 K reveals an upward energetic shift of the surface state native to Ag(111) from a band edge of -67 meV on the clean surface to +82.5 meV recorded over adenine islands. Differential conductance images show the impact of adenine domains on the density of available states as a function of energy relative to the uncovered Ag terraces as well as free-electron-like scattering in the adenine domains. Dispersion of the parallel wave vector of scattered electrons in the adenine domains is compared with the dispersion for electron scattering in bare silver and the ratio of effective masses for electrons in those bands is 1.1+/-0.2. It is hypothesized that this shift occurs due to a combination of effects brought on by the adsorption of adenine including dielectric screening of the first image potential.

Modification of Ag(111) surface electronic structure via weak molecular adsorption of adenine measured with low temperature scanning tunneling microscopy and spectroscopy.

The binding configuration of propylene glycol stereoisomer molecules adsorbed on the Si(001)-2×1 surface was investigated using a combination of scanning tunneling microscopy (STM) and density functional theory calculations. Propylene glycol was found to adsorb dissociatively via two hydroxyl groups exclusively as a bridge between the ends of two adjacent dimers along the dimer row. The chirality was preserved during bonding to Si atoms and was identifiable with STM imaging. The large number of propylene glycol conformers in the gas phase was reduced to a single configuration adsorbed on the surface at low molecular coverage.

Binding structures of propylene glycol stereoisomers on the Si(001)-2×1 surface: a combined scanning tunneling microscopy and theoretical study.

Chemical warfare agent simulants are often used as an agent surrogate to perform environmental testing, mitigating exposure hazards. This work specifically addresses the assessment of downwind agent vapor concentration resulting from an evaporating simulant droplet. A previously developed methodology was used to estimate the mass diffusivities of the chemical warfare agent simulants methyl salicylate, 2-chloroethyl ethyl sulfide, di-ethyl malonate, and chloroethyl phenyl sulfide. Along with the diffusivity of the chemical warfare agent bis(2-chloroethyl) sulfide, the simulant diffusivities were used in an advection-diffusion model to predict the vapor concentrations downwind from an evaporating droplet of each chemical at various wind velocities and temperatures. The results demonstrate that the simulant-to-agent concentration ratio and the corresponding vapor pressure ratio are equivalent under certain conditions. Specifically, the relationship is valid within ranges of measurement locations relative to the evaporating droplet and observation times. The valid ranges depend on the relative transport properties of the agent and simulant, and whether vapor transport is diffusion or advection dominant.

Thomas P. Pearl

OptiMetrics, Inc., a DCS Company

An Inverse Analysis Approach to the Characterization of Chemical Transport in Paints