The development of calibrants through characterization of volatile organic compounds from peroxide based explosives and a non-target chemical calibration compound

Detection canines represent the fastest and most versatile means of illicit material detection. This research endeavor in its most simplistic form is the improvement of detection canines through training, training aids, and calibration. This study focuses on developing a universal calibration compound for which all detection canines, regardless of detection substance, can be tested daily to ensure that they are working with acceptable parameters. Surrogate continuation aids (SCAs) were developed for peroxide based explosives along with the validation of the SCAs already developed within the International Forensic Research Institute (IFRI) prototype surrogate explosives kit. Storage parameters of the SCAs were evaluated to give recommendations to the detection canine community on the best possible training aid storage solution that minimizes the likelihood of contamination. Two commonly used and accepted detection canine imprinting methods were also evaluated for the speed in which the canine is trained and their reliability. As a result of the completion of this study, SCAs have been developed for explosive detection canine use covering: peroxide based explosives, TNT based explosives, nitroglycerin based explosives, tagged explosives, plasticized explosives, and smokeless powders. Through the use of these surrogate continuation aids a more uniform and reliable system of training can be implemented in the field than is currently used today. By examining the storage parameters of the SCAs, an ideal storage system has been developed using three levels of containment for the reduction of possible contamination. The developed calibration compound will ease the growing concerns over the legality and reliability of detection canine use by detailing the daily working parameters of the canine, allowing for Daubert rules of evidence admissibility to be applied. Through canine field testing, it has been shown that the IFRI SCAs outperform other commercially available training aids on the market. Additionally, of the imprinting methods tested, no difference was found in the speed in which the canines are trained or their reliability to detect illicit materials. Therefore, if the recommendations discovered in this study are followed, the detection canine community will greatly benefit through the use of scientifically validated training techniques and training aids.

Application of biomarkers and compound specific stable isotopes for the assessment of hydrology as a driver of organic matter dynamics in the Everglades ecosystem

The Everglades is a sub-tropical coastal wetland characterized among others by its hydrological features and deposits of peat. Formation and preservation of organic matter in soils and sediments in this wetland ecosystem is critical for its sustainability and hydrological processes are important divers in the origin, transport and fate of organic matter. With this in mind, organic matter dynamics in the greater Florida Everglades was studied though various organic geochemistry techniques, especially biomarkers, bulk and compound specific δ13C and δD isotope analysis. The main objectives were focused on how different hydrological regimes in this ecosystem control organic matter dynamics, such as the mobilization of particulate organic matter (POM) in freshwater marshes and estuaries, and how organic geochemistry techniques can be applied to reconstruct Everglades paleo-hydrology. For this purpose organic matter in typical vegetation, floc, surface soils, soil cores, and estuarine suspended particulates were characterized in samples selected along hydrological gradients in the Water Conservation Area 3, Shark River Slough and Taylor Slough. ^ This research focused on three general themes: (1) Assessment of the environmental dynamics and source-specific particulate organic carbon export in a mangrove-dominated estuary. (2) Assessment of the origin, transport and fate of organic matter in freshwater marsh. (3) Assessment of historical changes in hydrological conditions in the Everglades (paleo-hydrology) though biomarkes and compound specific isotope analyses. This study reports the first estimate of particulate organic carbon loss from mangrove ecosystems in the Everglades, provides evidence for particulate organic matter transport with regards to the formation of ridge and slough landscapes in the Everglades, and demonstrates the applicability of the combined biomarker and compound-specific stable isotope approach as a means to generate paleohydrological data in wetlands. The data suggests that: (1) Carbon loss from mangrove estuaries is roughly split 50/50 between dissolved and particulate carbon; (2) hydrological remobilization of particulate organic matter from slough to ridge environments may play an important role in the maintenance of the Everglades freshwater landscape; and (3) Historical changes in hydrology have resulted in significant vegetation shifts from historical slough type vegetation to present ridge type vegetation. ^

Evaluation of the Scent Collection System for Its Effectiveness in Volatile Organic Compound Collection and Use in Canine Training

As a result of increased terrorist activity around the world, the development of a canine training aid suitable for daily military operations is necessary to provide effective canine explosive detection. Since the use of sniffer dogs has proven to be a reliable resource for the rapid detection of explosive volatiles organic compounds, the present study evaluated the ability of the Human Scent Collection System (HSCS) device for the creation of training aids for plasticized / tagged explosives, nitroglycerin and TNT containing explosives, and smokeless powders for canine training purposes. Through canine field testing, it was demonstrated that volatiles dynamically collected from real explosive material provided a positive canine response showing the effectiveness of the HSCS in creating canine training aids that can be used immediately or up to several weeks (3) after collection under proper storage conditions. These reliable non-hazardous training aids allow its use in areas where real explosive material aids are not practical and/or available.

EPI-001, a compound active against castration-resistant prostate cancer, targets transactivation unit 5 of the androgen receptor

ACKNOWLEDGEMENTS We thank J. M. Valverde (IRB) as well as the NMR facilities of the University of Barcelona (CCiT UB) and the Instituto de Química Física Rocasolano (IQFR, CSIC) for their assistance in, respectively, protein production and NMR. This work was supported by IRB, ICREA (X.S.), Obra Social “la Caixa” (Fellowship to E.D.M. and CancerTec grants to X.S.) MICINN (CTQ2009-08850 to X.S.), MINECO (BIO2012-31043 to X.S.; CTQ2014-56361-P to A.R), Marató de TV3 (102030 to X.S. and 102031 to E.E.P) the COFUND programme of the European Commission (C.T.W.P., A. R. and X.S.), the European Research Council (CONCERT, contract number 648201, to X.S.), the Ramón y Cajal program of MICINN (RYC-2011-07873 to C.W.B.) the Serra Hunter Programme (E.E.P.) and AGAUR (SGR-2014-56RR14 to E.E.P). IRB Barcelona is the recipient of a Severo Ochoa Award of Excellence from MINECO (Government of Spain)

Investigation of electrically active defects at the interface of high-k dielectrics and compound semiconductors

As silicon based devices in integrated circuits reach the fundamental limits of dimensional scaling there is growing research interest in the use of high electron mobility channel materials, such as indium gallium arsenide (InGaAs), in conjunction with high dielectric constant (high-k) gate oxides, for Metal-Oxide-Semiconductor Field Effect Transistor (MOSFET) based devices. The motivation for employing high mobility channel materials is to reduce power dissipation in integrated circuits while also providing improved performance. One of the primary challenges to date in the field of III-V semiconductors has been the observation of high levels of defect densities at the high-k/III-V interface, which prevents surface inversion of the semiconductor. The work presented in this PhD thesis details the characterization of MOS devices incorporating high-k dielectrics on III-V semiconductors. The analysis examines the effect of modifying the semiconductor bandgap in MOS structures incorporating InxGa1-xAs (x: 0, 0.15. 0.3, 0.53) layers, the optimization of device passivation procedures designed to reduce interface defect densities, and analysis of such electrically active interface defect states for the high-k/InGaAs system. Devices are characterized primarily through capacitance-voltage (CV) and conductance-voltage (GV) measurements of MOS structures both as a function of frequency and temperature. In particular, the density of electrically active interface states was reduced to the level which allowed the observation of true surface inversion behavior in the In0.53Ga0.47As MOS system. This was achieved by developing an optimized (NH4)2S passivation, minimized air exposure, and atomic layer deposition of an Al2O3 gate oxide. An extraction of activation energies allows discrimination of the mechanisms responsible for the inversion response. Finally a new approach is described to determine the minority carrier generation lifetime and the oxide capacitance in MOS structures. The method is demonstrated for an In0.53Ga0.47As system, but is generally applicable to any MOS structure exhibiting a minority carrier response in inversion.

Weak coupling of acoustic-like phonons and magnon dynamics in incommensurate spin ladder compound Sr14Cu24O41

Intriguing lattice dynamics has been predicted for aperiodic crystals that contain incommensurate substructures. Here we report inelastic neutron scattering measurements of phonon and magnon dispersions in Sr14Cu24O41, which contains incommensurate one-dimensional (1D) chain and two-dimensional (2D) ladder substructures. Two distinct acoustic phonon-like modes, corresponding to the sliding motion of one sublattice against the other, are observed for atomic motions polarized along the incommensurate axis. In the long wavelength limit, it is found that the sliding mode shows a remarkably small energy gap of 1.7-1.9 meV, indicating very weak interactions between the two incommensurate sublattices. The measurements also reveal a gapped and steep linear magnon dispersion of the ladder sublattice. The high group velocity of this magnon branch and weak coupling with acoustic phonons can explain the large magnon thermal conductivity in Sr14Cu24O41 crystals. In addition, the magnon specific heat is determined from the measured total specific heat and phonon density of states, and exhibits a Schottky anomaly due to gapped magnon modes of the spin chains. These findings offer new insights into the phonon and magnon dynamics and thermal transport properties of incommensurate magnetic crystals that contain low-dimensional substructures.

n-Alkane content and compound-specific d13C values of soil samples, river samples, and marine surface samples

Southwestern Africa's coastal marine mudbelt, a prominent Holocene sediment package, provides a valuable archive for reconstructing terrestrial palaeoclimates on the adjacent continent. While the origin of terrestrial inorganic material has been intensively studied, the sources of terrigenous organic material deposited in the mudbelt are yet unclear. In this study, plant wax derived n-alkanes and their compound-specific d13C in soils, flood deposits and suspension loads from regional fluvial systems and marine sediments are analysed to characterize the origin of terrestrial organic material in the southwest African mudbelt. Soils from different biomes in the catchments of the Orange River and small west coast rivers show on average distinct n-alkane distributions and compound-specific d13C values reflecting biome-specific vegetation types, most notably the winter rainfall associated Fynbos Biome of the southwestern Cape. In the fluvial sediment samples from the Orange River, changes in the n-alkane distributions and compound-specific d13C compositions reveal an overprint by local vegetation along the river's course. The smaller west coast rivers show distinct signals, reflecting their small catchment areas and particular vegetation communities. Marine surface sediments spanning a transect from the northern mudbelt (29°S) to St. Helena Bay (33°S) reveal subtle, but spatially coherent, changes in n-alkane distributions and compound-specific d13C, indicating the influence of Orange River sediments in the northern mudbelt, the increasing importance of terrigenous input from the adjacent western coastal biomes in the central mudbelt, and contributions from the Fynbos Biome to the southern mudbelt. These findings indicate the different sources of terrestrial organic material deposited in the mudbelt, and highlight the potential the mudbelt has to preserve evidence of environmental change from the adjacent continent.

Refractometry Studies of the Optical Properties of Polymer Films and the Development of Polymer Coated Refractive Index Sensors

Sensors for real-time monitoring of environmental contaminants are essential for protecting ecosystems and human health. Refractive index sensing is a non-selective technique that can be used to measure almost any analyte. Miniaturized refractive index sensors, such as silicon-on-insulator (SOI) microring resonators are one possible platform, but require coatings selective to the analytes of interest. A homemade prism refractometer is reported and used to characterize the interactions between polymer films and liquid or vapour-phase analytes. A camera was used to capture both Fresnel reflection and total internal reflection within the prism. For thin-films (d = 10 μm - 100 μm), interference fringes were also observed. Fourier analysis of the interferogram allowed for simultaneous extraction of the average refractive index and film thickness with accuracies of ∆n = 1-7 ×10-4 and ∆d < 3-5%. The refractive indices of 29 common organic solvents as well as aqueous solutions of sodium chloride, sucrose, ethylene glycol, glycerol, and dimethylsulfoxide were measured at λ = 1550 nm. These measurements will be useful for future calibrations of near-infrared refractive index sensors. A mathematical model is presented, where the concentration of analyte adsorbed in a film can be calculated from the refractive index and thickness changes during uptake. This model can be used with Fickian diffusion models to measure the diffusion coefficients through the bulk film and at the film-substrate interface. The diffusion of water and other organic solvents into SU-8 epoxy was explored using refractometry and the diffusion coefficient of water into SU-8 is presented. Exposure of soft baked SU-8 films to acetone, acetonitrile and methanol resulted in rapid delamination. The diffusion of volatile organic compound (VOC) vapours into polydimethylsiloxane and polydimethyl-co-polydiphenylsiloxane polymers was also studied using refractometry. Diffusion and partition coefficients are reported for several analytes. As a model system, polydimethyl-co-diphenylsiloxane films were coated onto SOI microring resonators. After the development of data acquisition software, coated devices were exposed to VOCs and the refractive index response was assessed. More studies with other polymers are required to test the viability of this platform for environmental sensing applications.

Level-resolved quantum statistical theory of electron capture into many-electron compound resonances in highly charged ions

The strong mixing of many-electron basis states in excited atoms and ions with open f shells results in very large numbers of complex, chaotic eigenstates that cannot be computed to any degree of accuracy. Describing the processes which involve such states requires the use of a statistical theory. Electron capture into these “compound resonances” leads to electron-ion recombination rates that are orders of magnitude greater than those of direct, radiative recombination and cannot be described by standard theories of dielectronic recombination. Previous statistical theories considered this as a two-electron capture process which populates a pair of single-particle orbitals, followed by “spreading” of the two-electron states into chaotically mixed eigenstates. This method is similar to a configuration-average approach because it neglects potentially important effects of spectator electrons and conservation of total angular momentum. In this work we develop a statistical theory which considers electron capture into “doorway” states with definite angular momentum obtained by the configuration interaction method. We apply this approach to electron recombination with W²⁰⁺, considering 2×10⁶ doorway states. Despite strong effects from the spectator electrons, we find that the results of the earlier theories largely hold. Finally, we extract the fluorescence yield (the probability of photoemission and hence recombination) by comparison with experiment.