Energetic materials encompass a wide range of chemical compounds all associated with a significant risk of fire and explosion. They include explosives, fireworks, pyrotechnics, powders, propellants and other unsteady chemicals. These materials store a high level of chemical energy and are able to release it rapidly without external contribution of oxygen or any other oxidizer. The behaviour of these materials in case of explosive detonations is relatively wellknown from empirical and practical points of view. However, fundamental scientific questions remain unanswered related to the mechanisms of heat release. The current understanding of these mechanisms lacks appropriate thermochemical characterisation. The aim of the study is the analysis of thermal and chemical characteristics of energetic materials under conditions that exclude detonations. Detonation is excluded in order to better isolate the thermal and chemical mechanisms involved in the burning process. The experimental work has been conducted using the FM Global Fire Propagation Apparatus (FPA) [ASTM E2058‐03]. One of the benefits of using this experimental apparatus rather than the Cone Calorimeter is that it allows controlling the feed of heat and oxidizer to the reaction zone. The material chosen to conduct experiments on is a ternary smoke powder based on a mixture of starch and lactose as fuel components and potassium nitrate as oxidizer. This product is currently used by fire brigades to assess smoke venting systems efficiency of buildings. The kinetics associated with the combustion of the material was assessed slow enough to allow measuring instruments to capture the thermal and chemical evolution during combustion reaction. Thermal analysis has first been carried out by means of DSC, TGA, DTA, MS and FTIR data in order to understand the decomposition of the material and its energetic evolution when undergoing heating. However, if the latter methods help defining the decomposing path of the material, they do not provide an integral view of its combustion behaviour, in particular, the emissions of toxics which are kinetic path dependent. Subsequently, combustion tests have been carried out using the FPA. Its ability to capture the evolution of gases emissions formed during the reaction has been proved. The influence of two configuration parameters on the combustion behaviour and on the gaseous emissions of the material has been investigated. The proportion fuel/oxidizer has been varied as well as the composition of the reacting atmosphere. Results shows that the quantity of oxidizer in the material affects the kinetics of the reactions taking place in the condense phase. Increasing the concentration of potassium nitrate in the mixture enhanced the reaction rate of the smouldering combustion. Higher quantity of volatiles is released which favoured the initiation of a diffusion flame regime in the gaseous phase, above the sample. While the kinetics of the condense phase is governed by the oxidizer concentration, experiments show that the flaming regime is influenced by the concentration of oxygen (O2) in the reacting atmosphere. A transition from diffusion to premixed flame is found when the concentration of O2 surrounding the sample is reduced below 18%. An analytical model has been used to explain the existence of a transition for a critical O2 concentration. Finally, thermal and combustion analyses have allowed to characterise the behaviour of the material under critical conditions, in terms of decomposition taking place in the condense phase but also potential toxic emissions that can be released. Toxicity, kinetics, temperature evolution do not provide a complete view of the combustion phenomenon. Beside these elements that characterise the behaviour of a material for given conditions as well as also the degree of fire hazard encountered, the energetic issue holds as an essential feature that cannot be neglected. The heat release rate (HRR) is a critical parameter that defines a fire. It does not constitute an intrinsic material property but it describes the energetic response of the couple formed by the material and its environment. Oxygen Consumption calorimetry (OC) and Carbon Dioxide Generation calorimetry (CDG) are widespread methods to calculate the HRR resulting from a combustion reaction. Apparatuses such as the FPA or the cone calorimeter have already proved their potential to qualify the burning behaviour of common fuels in addition to polymers when their data are combined with an adapted calorimetric procedure. The same approach has been applied to energetic materials. However, prior to using these techniques, it is fundamental to have identified their restrictions. These techniques provide approximate estimations of the HRR. Results are affected by the propagation of uncertainties. Several sources of uncertainties can be found. One can cite: 1. Uncertainties associated with the sample material; 2. Uncertainties associated with the test conditions; 3. Uncertainties associated with the measurements; 4. Uncertainties associated with calculation assumptions. If uncertainties cannot always be estimated, the three first sources cited have received attention in the past from the scientific community, alike the last one. The restrictions associated with the assumptions developed for using the OC and CDG principles have to be clarified. The limits of validity of the hypotheses have to be clearly defined. In particular, the present dissertation questions the relevance of the energy constants that have been specified for OC and CDG as well as their related uncertainties. One of the purposes of the research deals with the ability to estimate accurate error bars for the calculation of the HRR. Once uncertainties related to the calorimetric methods are assessed, a method adapted from the basic OC and CDG principles is introduced that allows estimating the HRR of energetic materials. The approach is based on considering the chemical decomposition of the burning compound and defining a fictitious molecule for which energy coefficients can be calculated. Nevertheless, it requires the material to be known. Finally, the question of the advantage brought by these techniques over others, in terms of accuracy, is discussed within the framework of unconventional products, such as energetic materials or compounds whose composition is ignored. The results from this work will contribute to the development of fireanalysis methodologies and validate their use with energetic materials.

Nephropathic cystinosis is a rare autosomal recessive disease characterised by raised lysosomal levels of cystine in the cells of almost all organs. It is treated by regular oral and topical administration of the aminothiol, cysteamine(Cystagon™), which possesses an offensive taste and smell. The oral form frequently causes emesis,and should be administered every six hours to be maximally effective. The topical eye drop treatment requires hourly application to be most effective.In an attempt to reduce this frequency and improve the treatment, the preparation and evaluation of three alternative cysteamine containing formulations (suppositories, long-acting ophthalmic gels and an inhaler) was undertaken. The physiochemical properties, stability and release profiles of the active (cysteamine or phe conjugate) from the formulations were evaluated. The suppositories released cysteamine over a 20-40 minute period with a T75= 10-13minutes. They were most stable at 4°C. The analysis of the ophthalmic gels demonstrated that a weak gel network was formed at low shear stress, the bioadhesion of the gel was increased with inclusion of a cysteamine derivative (e.g.mean force of 0.067N compared to 0.107N with compound included) and eight-hour, first order release from the gel was observed. There was significant adhesion observed between the ophthalmic gels and bovine corneal tissue. The pulmonary microspheres were spherical and within the optimum size range for deep lung delivery (1-5μm). However, Andersen Cascade Impactor analysis revealed poor deep lung penetration. In conclusion, these results demonstrated that more development work was required to produce a useful pulmonary formulation of cysteamine, however, formulation of an ocular applicable gel or suppository was readily achievable. The suppository preparations may be particularly beneficial for the treatment of infants, whilst the ophthalmic gel preparations could be developed for daily or overnight use. With respect to pulmonary delivery, microspheres in the optimum size range were produced. However, deep lung targeting was prevented by static agglomeration, which requires further investigation.

In this study we determined the magnitude of plant mediated CH4 emission (flux) in two vegetation types of Carex ramenskii. The objectives of this paper were to quantify the proportion of CH4 emissions from plant mediated flux and the total flux (plant and soil). This information is needed in order to understand how grazing affects plant mediated CH4 flux. In addition, we differentiated between two vegetation morphs, grazed and ungrazed, and determined the plant mediated CH4 flux for vegetation type.  This study was conducted at a field site on the Tutakoke River (61 15’N, 165 30’W) which is located in the coastal region of the Yukon-Kuskokwim Delta. Three replicate plots of the two vegetation morphs of Carex ramenskii were established. Methane flux was measured with a total flux chamber (plant and soil) and a single leaf chamber using a Picarro Cavity Ring-Down Spectroscopy Analyzer (Model G2308, Picarro Inc., Santa Clara, California). Plant density for the two plant types was determined. Temperature measurements were taken and correlated with gas flux. This study found that total net CH4 emissions from Carex ssp. were the same in both vegetation types. This similarity could indicate that plant mediated flux through vegetation is not affected by grazing in the sense that grazing is neither facilitating nor inhibiting plant mediated CH4 flux. The magnitude of plant mediated flux was still greater in the ungrazed meadow type, indicating on both greater facilitation of CH4 flux, and below ground oxygen transport enabling higher rates of CH4 consumption.

We apply a combination of suppression and release criteria to reconstruct the disturbance history of a ponderosa pine – Douglas-fir stand in central Idaho. In this stand, disturbance, likely fire, induced growth releases in some trees, and sudden, severe suppressions in others. To characterize growth release following disturbance, we developed boundary-line release criteria for Douglas-fir and ponderosa pine. Suppression criteria were applied to identify disturbances defined as a growth reduction of more than 1.8 standard deviations sustained for a minimum of five years. To prevent confusing a true release event with growth increases associated with recovery from suppression, release events were not tallied for at least fifteen years following a suppression event. Release and suppression events were combined to create a disturbance chronology characterized by a high frequency of disturbance between 1820 and 1920. This period of disturbance likely reflects post-European settlement land uses such as grazing and logging as well as an increase in fire frequency. Fire suppression in the latter part of the 20th Century likely explains the decrease in disturbance after 1940. We believe that a combination of release as well as suppression criteria best describes the disturbance history of this stand.

I investigate whether management’s decision to release or maintain the valuation allowance for deferred tax assets provides incremental information regarding pretax earnings growth in the following earnings period. I classify firm-years into two categories; valuation allowance release firm-years and valuation allowance maintain firm-years. The results of this study suggest that a release of the valuation allowance in the current period is positively associated with pretax earnings growth in the following period. This paper also studies whether a release of the valuation allowance yields increased external monitoring, and finds evidence that suggests an association.

Luminescent semiconductor quantum dots (QDs) are extensively researched for use in biological applications. They have unique optical and physical properties that make them excellent candidates to replace conventional organic dyes for cellular labeling, multiplexing, nucleic acid detection, and as generalized probes. The primary focus of this dissertation was to utilize quantum dots for improvement in immunoassays. Specifically, atherosclerosis biomarkers were detected simultaneously in an effort to demonstrate advances in early detection diagnostics. Quantum dot-antibody bioconjugates were prepared by encapsulation into mesoporous silica and functionalized with thiol and amine groups to enable bioconjugation. Functionalization of the mesoporous silica quantum dot composites facilitated biocompatibility for use with biological buffers in immunoassays. These bioconjugates were used in a sandwich immunoassay to detect atherosclerosis biomarkers IL-15 and MCP-1. Sandwich assays employ capture antibodies immobilized onto a well plate to bind as much of the antigen as possible. The capture antibodies increased binding by at least 4 times the amount of antigen bound to the surface of a direct detection assay. The sandwich immunoassay was able to detect 1 pg/mL of IL-15 and 50 pg/mL of MCP-1 biomarkers. Human serum albumin nanoparticles (HSAPs) were synthesized via a desolvation and crosslinking method. Human serum albumin is a versatile protein being used in a variety of applications. Quantum dots were loaded into HSAPs as potential detection probes for immunoassays. Efficient loading was not achieved, and the assay was unable to improve current detection limits. Controlled release studies were explored using HSAPs loaded with superparamagnetic iron oxide nanoparticles and a fluorescent drug analog. Exposure to a magnetic field resulted in degradation of the HSAPs. The fluorophore was released and measured to examine how cancer drugs might be controlled through a magnetic field. Gold nanorods and an anticancer drug, Sorafenib, were also encapsulated into HSAPs for treatment of renal cell carcinoma in vivo. Laser irradiation treatment combined with Sorafenib resulted in 100% tumor necrosis and total elimination of any viable tumor present. HSAPs have demonstrated remarkable potential as drug delivery nanocarriers.

Background: Migrant farmworkers are among the highest-risk populations for latent TB infection (LTBI) in the United States with numerous barriers to healthcare access and increased vulnerability to infectious diseases. LTBI is usually diagnosed on the border using the tuberculin skin test (TST). QuantiFERON-TB Gold In-Tube (QFT-GIT) also measures immune response against specific Mycobacterium tuberculosis antigens. The objective of this study is to assess the comparability of TST and QFT-GIT to detect LTBI among migrant farmworkers on the border, as well as to examine the effects of various demographic and clinical factors on test positivity. Methods: Participants were recruited using mobile clinics on the San Luis US-Mexico border and tested with QFT-GIT and TST. Demographic profiles and clinical histories were collected. Kappa coefficients assessed agreement between TST and QFT-GIT using various assay cutoffs. Logistic regression examined factors associated with positive TST or QFT-GIT results. Results: Of 109 participants, 59 of 108 (55 %) were either TST (24/71, 34 %) or QFT-GIT (52/106, 50 %) positive. Concordance between TST and QFT-GIT was fair (71 % agreement,kappa= 0.38, 95 % CI: 0.15, 0.61). Factors associated with LTBI positivity included smoking (OR = 1.26, 95 % CI-1.01-1.58) and diabetes/high blood sugar (OR = 0.70, 95 % CI = 0.51-0.98). Discussion: Test concordance between the two tests was fair, with numerous discordant results observed. Greater proportion of positives detected using QFT-GIT may help avoid LTBI under-diagnosis. Assessment of LTBI status on the border provides evidence whether QFT-GIT should replace the TST in routine practice, as well as identifies risk factors for LTBI among migrant populations.

Minimizing adhesion of ice has been the subject of extensive studies for applications such aircraft wings, wind turbine blades spacecraft, power transmission wires, while a growing interest concerns coatings for aerospace applications. The work described here describes progress for coatings and ice release test method development over the last few years. Major achievements include: (1) New Rigid Adherent-Resistant Elastomers (RARE), (2) A new Epoxied Cylinder (EC) adhesion test, (3) Validation of an ice release test, and (4) Study of ice adhesion strength on coating thickness for a PDMS elastomer. Rigid Adhesion-Resistance Elastomers (RARE) are comprised of 3F 1 terminated with triethoxysilane moieties and linear 3F polyurethane (U-3F). Hybrid compositions U-3F-x are designated by polyurethane weight percent “x”. Interestingly, RARE coatings spontaneously “self-stratify” during coating deposition and cure. Cured RARE coatings are comprised of (1) a nanoscale surface layer with low work of adhesion, (2) a low modulus mesoscale and (3) a tough U-3F bulk, where “Mesoscale” is defined as a near surface region with a depth ~ 1000 nm. An EC adhesion test was developed to evaluate the fouling release characteristics of RARE. EC adhesion testing was devised by using the commercially available instrument, TA RSA-3. The TA RSA-3 is well suited for these tests as the 3.5 kg load cell facilitates accurate measurements. This test gives peak force (Ps) for EC removal. A striking compositional dependence was found for EC adhesion. A U-3F-50 hybrid coating had the lowest adhesion (Ps = 0.078 MPa) with good toughness (6.2 MPa). Bulk and surface characterization together with adhesion measurements established U-3F-x hybrid coatings, and U-3F-50 in particular, as new fluorous rigid adherent-resistant elastomers (RARE) that are tough, oil resistant, and optically transparent. Inspired by the Epoxied Cylinder (EC) adhesion test, a laboratory method for ice adhesion measurement with a commercially available instrument was established in the Wynne Laboratory. This is the first laboratory ice adhesion test that does not require a custom built apparatus. The temperature controlled chamber on TA RSA-3 is an enabling feature that is essential for the test. The method involves removal of an ice cylinder from a polymer coating with a probe and the determination of peak removal force (Ps). To validate the test method, the strength of ice adhesion was determined for a prototypical glassy polymer, poly(methyl methacrylate). The distance of the probe from the PMMA surface has been identified as a critical variable for Ps. The new test provides a readily available platform for investigating fundamental surface characteristics affecting ice adhesion. In addition to the ice release test, PMMA coatings were characterized using DSC, DCA and TM-AFM. This new laboratory ice release test was then employed to obtain the thickness dependence of ice adhesion for Sylgard 184, a filled polydimethylsiloxane elastomer. A correlation between ice adhesion and coating thickness (t) was found, that follows a relationship developed by Kendall over 40 years ago for removal of a rigid object from an elastomer. In particular, a nearly linear relationship between peak removal stress (Ps) and 1/t1/2 was found, with Ps decreasing from 550 kPa to 100 kPa with coating thickness increasing from 12 μm to 800 μm. While work of adhesion, which is related to surface free energy, is recognized as an important factor that can affect ice release, the results reported herein show that coating thickness can override this single parameter for elastomeric substrates. Base on the result, a general model is proposed for the removal of ice from low modulus elastomers (~10 MPa).

Female offenders often have had increased financial difficulties post-release because of lower levels of educational achievement and less job experience. Career programming may prove useful to female offenders by providing guidance with career decisions and strengthening career decision-making skills. The aims of this study were to investigate career decision-making skills and self-efficacy in the context of vocational programming for a group of female offenders. A pretest-posttest quasi-experimental design was used to examine scale scores for a group who participated in programming and a control group at the same correctional facility. A series oft tests revealed no significant differences between the control and intervention groups. An examination of the subscale means indicated that female offenders may advocate more passive decision-making styles and lower career decision-making self-efficacy than the original norm samples for these instruments.

Characterization of in vitro and in vivo drug release profiles constitutes an important step in developing and optimizing an effective, long acting delivery system for naltrexone. Accelerated in vitro methods are also important for quality assurance of manufactured dosage forms. For drug release testing of sustained release parenteral dosage forms, the modified USP Apparatus 4 (flow-through cell) has been recommended by the The Fédération Internationale Pharmaceutique/American Association of Pharmaceutical Scientists (FIP/AAPS) Guidelines. Details on such studies however, are generally not found in the literature. To incorporate 'biorelevance' to implant drug release studies, this research investigated an approach to apparatus design and media selection that is significantly different from conventional dissolution studies involving oral dosage forms.Biodegradable implants of naltrexone were obtained from Durect Corporation, USA. A modified Hanks' Balanced Salts Solution was characterized as a 'biorelevant' medium for in vitro drug release studies. Naltrexone was found to be sufficiently stable in the medium, as determined by a stability-indicating High Performance Liquid Chromatography (HPLC) assay. A miniature, cell-culture, capillary system was modified and tested as a 'biorelevant' alternative to the modified flow-through apparatus, to mimic significant barriers to drug release that would be expected in vivo. The in vitro release profiles generated up to 3 months using both devices indicated considerable (2-fold) variation in rates, as expected from the difference in media flow characteristics. An implantation study in a dog was conducted to determine which of the two devices could provide a better simulation of the in vivo conditions. Analysis of in vivo samples was carried out by a Liquid Chromatography-Tandem Mass Spectrometry (LC-MS-MS) method that also employed a molecular model approach to demonstrate the absence of Internal Standard Deuterium Isotope Effects. A good In vitro-In vivo Correlation (IVIVC) resulted from both devices; however, the capillary device provided a superior simulation for the lag-time in absorption. The accelerated study at 45°C and 55°C established a predictable increase in release rates (2-fold and 4-fold increases, respectively). The approach described in this work could provide the basis for future method modification of in vitro drug release tests of subcutaneous implants.