In situ measurements of subsurface contaminants with a multi-channel laser-induced fluorescence system.

A new multi-channel laser-induced fluorescence (LIF) probe with novel optical fiber probe geometry has been designed and integrated into a cone penetrometer testing (CPT) system for in situ contamination detection. The system is capable of collecting excitation and emission matrices (EEMs) of subsurface contaminants as a function of depth in seconds. Compared to our previous multi-channel LIF-CPT system, the new system is faster and more compact, with reduced probe size and sampling area. This article describes the first field demonstration of the system at Hanscom Air Force Base, Massachusetts. One contaminated site within the base was characterized through in situ measurements of 26 LIF-CPT pushes. To validate the LIF results, core samples taken at five locations were analyzed by both on-site LIF measurements and by off-site laboratory analyses with EPA methods. The comparison of the LIF and laboratory results is presented, along with the results of the in situ measurements.     

Determination of ferrous and ferric iron in aqueous biological solutions

A solvent extraction method was employed to determine ferrous and ferric iron in aqueous samples. Fe³⁺ is selectively extracted into the organic phase (n-heptane) using HDEHP (bis(2-ethylhexyl) hydrogen phosphate) and is then stripped using a strong acid. After separation, both oxidation states and the total iron content were determined directly by ICP-MS analysis. This extraction method was refined to allow determination of both iron oxidation states in the presence of strong complexing ligands, such as citrate, NTA and EDTA. The accuracy of the method was verified by crosschecking using a refinement of the ferrozine assay. Presented results demonstrate the ability of the extraction method to work in a microbiological system in the presence of strong chelating agents following the bioreduction of Fe³⁺ by the Shewanella alga BrY. Based on the results we report, a robust approach was defined to separately analyze Fe³⁺ and Fe²⁺ under a wide range of potential scenarios in subsurface environments where radionuclide/metal contamination may coexist with strongly complexing organic contaminants.     

Realization of quantum-dot cellular automata using semiconductor quantum dots

We demonstrate that a quantum-dot cellular automata device can be fabricated using electron beam lithographically defined gates on GaAs/AlGaAs heterostructure materials, and that by tuning the four quantum dot (J. Phys. C: Solid State Phys. 21 (1988) L893) system polarization of one double dot can lead to polarization in the neighboring double dot (Phys. Rev. B 67 (2003) 033302). The polarization is detected using a 1-D or 0-D channel defined next to one pair of double dots which acts as a non-invasive voltage probe (Phys. Rev. Lett. 70 (1993) 1311). Ultimately a cellular automata device should be isolated from reservoirs to prevent charge fluctuations caused by co-tunneling. The non-invasive voltage probe is used to show that coupled double dots isolated from reservoirs can be made to have a sharper polarization transition. By studying the broadening of the polarization signal from a coupled double dot system isolated from reservoirs, we deduce the charge dephasing times for intra dot scattering to be more than 0.2 ns (Phys. Rev. B 67 (2003) 073302).     

Using engineered single-chain antibodies to correlate molecular binding properties and nanoparticle adhesion dynamics

Elucidation of the relationship between targeting molecule binding properties and the adhesive behavior of therapeutic or diagnostic nanocarriers would aid in the design of optimized vectors and lead to improved efficacy. We measured the adhesion of 200-nm-diameter particles under fluid flow that was mediated by a diverse array of molecular interactions, including recombinant single-chain antibodies (scFvs), full antibodies, and the avidin/biotin interaction. Within the panel of scFvs, we used a family of mutants that display a spectrum of binding kinetics, allowing us to compare nanoparticle adhesion to bond chemistry. In addition, we explored the effect of molecular size by inserting a protein linker into the scFv fusion construct and by employing scFvs that are specific for targets with vastly different sizes. Using computational models, we extracted multivalent kinetic rate constants for particle attachment and detachment from the adhesion data and correlated the results to molecular binding properties. Our results indicate that the factors that increase encounter probability, such as adhesion molecule valency and size, directly enhance the rate of nanoparticle attachment. Bond kinetics had no influence on scFv-mediated nanoparticle attachment within the kinetic range tested, however, but did appear to affect antibody/antigen and avidin/biotin mediated adhesion. We attribute this finding to a combination of multivalent binding and differences in bond mechanical strength between recombinant scFvs and the other adhesion molecules. Nanoparticle detachment probability correlated directly with adhesion molecule valency and size, as well as the logarithm of the affinity for all molecules tested. On the basis of this work, scFvs can serve as viable targeting receptors for nanoparticles, but improvements to their bond mechanical strength would likely be required to fully exploit their tunable kinetic properties and maximize the adhesion efficiency of nanoparticles that bear them.     

Predicting the solubility of xenon in n-hexane and n-perfluorohexane: a simulation and theoretical study

The solubility of xenon in n-hexane and n-perfluorohexane has been studied using both molecular simulation and a version of the SAFT approach (SAFT-VR). The calculations were performed close to the saturation line of each solvent, between 200 K and 450 K, which exceeds the smaller temperature range where experimental data are available in the literature. Molecular dynamics simulations, associated with Widom's test particle insertion method, were used to calculate the residual chemical potential of xenon in n-hexane and n-perfluorohexane and the corresponding Henry's law coefficients. The simulation results overestimate the solubility of xenon in both solvents when simple geometric combining rules are used, but are in good agreement if a binary interaction parameter is included. With the SAFT-VR approach we are able to reproduce the experimental solubility for xenon in n-hexane, using simple Lorentz-Berthelot rules to describe the unlike interaction. In the case of n-perfluorohexane as a solvent, a binary interaction parameter was introduced, taken from previous work on (xe + C₂F₆) mixtures. Overall, good agreement is obtained between the simulation, theoretical and experimental data.     

Spin-incoherent transport in quantum wires

When a quantum wire is weakly confined, a conductance plateau appears at e;{2}/h with decreasing carrier density in zero magnetic field accompanied by a gradual suppression of the 2e;{2}/h plateau. Applying an in-plane magnetic field B_{ parallel} does not alter the value of this quantization; however, the e;{2}/h plateau weakens with increasing B_{ parallel} up to 9 T, and then strengthens on further increasing B_{ parallel}, which also restores the 2e;{2}/h plateau. Our results are consistent with spin-incoherent transport in a one-dimensional wire.     

Low-temperature collapse of electron localization in two dimensions

We report direct experimental evidence that the insulating phase of a disordered, yet strongly interacting two-dimensional electron system becomes unstable at low temperatures. As the temperature decreases, a transition from insulating to metal-like transport behavior is observed, which persists even when the resistivity of the system greatly exceeds the quantum of resistivity h/e2. The results have been achieved by measuring transport on a mesoscopic length scale while systematically varying the strength of disorder.