Publications

Tethered supramolecular machines represent a new class of active self-assembled monolayers in which molecular configurations can be reversibly programmed using electrochemical stimuli. We are using these machines to address the chemistry of substrate surfaces for integrated microfluidic systems. Interactions between the tethered tetracationic cyclophane host cyclobis(paraquat-p-phenylene) and dissolved {pi}-electron-rich guest molecules, such as tetrathiafulvalene, have been reversibly switched by oxidative electrochemistry. The results demonstrate that surface-bound supramolecular machines can be programmed to adsorb or release appropriately designed solution species for manipulating surface chemistry.

Sandia National Laboratories has sponsored an LDRD (Laboratory Directed Research and Development) project to investigate and develop micro-chemical sensors for in-situ monitoring of subsurface contaminants. As part of this project, a literature search has been conducted to survey available technologies and identify the most promising methods for sensing and monitoring subsurface contaminants of interest. Specific sensor technologies are categorized into several broad groups, and these groups are then evaluated for use in subsurface, long-term applications. This report introduces the background and specific scope of the problem being addressed by this LDRD project, and it provides a summary of the advantages and disadvantages of each sensor technology identified from the literature search.

A range of pore diffusivities, D{sub p}, is implied by the high degree of pore-scale heterogeneity observed in core samples of the Culebra (dolomite) Member of the Rustler formation, NM. Earlier tracer tests in the culebra at the field-scale have confirmed significant heterogeneity in diffusion rate coefficients (the combination of D{sub p} and matrix block size). In this study, expressions for solute diffusion in the presence of multiple simultaneous matrix diffusivities are presented and used to model data from eight laboratory-scale diffusion experiments performed on five Culebra samples. A lognormal distribution of D{sub p} is assumed within each of the lab samples. The estimated standard deviation ({sigma}{sub d}) of In(D{sub p}) within each sample ranges from 0 to 1, with most values lying between 0.5 and 1. The variability over all samples leads to a combined {sigma}{sub d} in the range of 1.0 to 1.2, which appears to be consistent with a best-fit statistical distribution of formation factor measurements for similar Culebra samples. A comparison of the estimation results to other rock properties suggests that, at the lab-scale, the geometric mean of D{sub p} increases with bulk porosity and the quantity of macroscopic features such as vugs and fractures. However, {sigma}{sub d} appears to be determined by variability within such macroscopic features and/or by micropore-scale heterogeneity. In addition, comparison of these experiments to those at larger spatial scales suggests that increasing sample volume results in an increase in {sigma}{sub d}.