The American Society of Civil Engineers’ (ASCE’s) “2013 Report Card for America’s Infrastructure” estimated that “32% of America’s major roads are in poor or mediocre condition.” An estimated $100 billion dollars are needed to maintain that condition, and an additional $79 billion is needed to improve the quality of American roadways to an acceptable level. In many regions around the US, the service lives of concrete pavements are limited by the damage caused by freezing and thawing of pore solution inside the pavements. Alkali-activated slags (AAS) are produced from ground granulated blast furnace slag (GGBFS), a byproduct of iron production, and exhibit cementitious properties. AAS concretes have been shown to have improved corrosion and freeze/thaw resistance compared to traditional cementbased concretes. A Guarded Longitudinal Comparative Calorimeter (GLCC) was used to determine when the freezing and thawing of internal water occurs in three AAS mortars using solutions of NaOH, Na2CO3, or waterglass compared to a control Ordinary Portland Cement (OPC) mortar. AAS mortars using NaOH and Na2CO3 showed comparable thermal properties to the OPC mortar using the GLCC, and the AAS mortar using waterglass was shown to have higher heat capacity compared to the other AAS mixes. The compressive strengths varied by the alkaline solution used, with AAS with Na2CO3 showing inferior compressive strength to OPC, AAS with NaOH showing similar compressive strength to OPC, and AAS with waterglass showing superior compressive strength to OPC, but poor workability. A computer model of the GLCC testing procedure was created and showed good agreement with the experimental data. The GLCC model can be modified to approximate the results of the GLCC using a wider range of materials and internal solutions, like PCMs.

Due to their small size and ectothermic biology, the heat production of insects and insect larvae is hard to quantify. However, knowing the amount of heat production, as well as ammonia production of insects may be beneficial for commercial production of valuable insect species. Black soldier fly larvae (BSFL) are of interest in the agricultural industry because they quickly consume organic waste and have high amounts of protein and fat in their bodies. It has been proposed that BSFL be used to manage livestock waste, while serving as a high-protein feed source for livestock animals. To efficiently rear BSFL, it is necessary to design rearing facilities, which maintain optimal conditions for the larvae. To design such a facility, it is necessary to know the amount of heat and ammonia that BSFL produce. A gradient calorimeter was used to measure the heat and ammonia production rates of black soldier fly larvae. The study determined that BSFL heat production changes significantly with the age and weight of the larvae. Aggregations produce the most total heat when larvae are older and larger. The study also found that larvae produce less heat per individual and per gram of body weight as they grow. Larvae also produce significantly different amounts of heat depending on the size of the groups they are in, and do not produce consistent amounts of heat per individual or per gram of body weight, even if maintained at a consistent population density. Larvae in group sizes of 100, 300, and 500 produced an average and standard deviation of 0.00107±0.000295, 0.00067±0.00014, and 0.00049±0.00020 W/larva, respectively. Likewise, larvae in groups of 100, 300 and 500 produced an average of 0.01826±0.00010, 0.01023±0.00565, and 0.00575±0.00371 W/g, respectively. The differences in heat produced per individual and per gram is troublesome when trying to estimate a total heat production for large populations. The largest heat production rate observed in this study was 0.407 W, and was produced by a group of 500 BSFL. Frass analysis indicated that between 4.80 and 7.79 lbs of ammoniacal-nitrogen is emitted for every ton of frass produced. These data could be used to estimate the total heat and ammonia produced from a larger population of BSFL being reared inside a closed facility, allowing engineers to design HVAC systems to keep the larvae at their optimal growing condition year-round. Placing BSFL rearing accommodations at livestock facilities could be beneficial to livestock, poultry, and fishery producers, because BSFL can be used to dispose of animal wastes and are also a good source of protein-rich animal feed.

Purpose. To investigate the validity of the Sense Wear Pro Armband (SWA) to measure energy expenditure (EE) in healthy participants using wheelchair ergometry as an exercise modality. Method. Minute by minute EE was measured simultaneously using the SWA and indirect calorimetry(IC) during three different wheeling speeds including self-selected speed (0.81 m/s), moderate speed (1.11 m/s), and fast speed (1.73 m/s). Results. Twenty healthy volunteers (age = 34.0 (5.8) years)participated. The intraclass correlation coefficients (ICCs) were 0.50 (p=0.010), 0.59 (p=0.003), and 0.68 (p=0.000) for the self-selected speed, moderate speed, and fast speed wheeling, respectively. The SWA overestimated EE 57.8%, 57.4 %, and 63.7% for self-selected speed, moderate speed, and fast speed, respectively. Conclusions. The SWA failed to provide an accurate estimate of EE as measured by indirect calorimetry for wheelchair ergometry exercise in healthy subjects. The SWA overestimated EE for all exercise intensities. / REHABILITATION SCIENCE-PHYSICAL THERAPY

Simultaneous measurements of energy and protein metabolism can provide valuable information about their interactions. Dietary lysine is limiting in typical feedstuffs fed to swine and, therefore, limits protein synthesis. Current recommendations for dietary amino acid and energy intakes may not be reflective of the requirements for modern, highly productive sows and, therefore, invalidate requirement estimates determined according to the factorial approach. Current feeding recommendations suggest a constant amino acid intake throughout gestation. However, the demands for amino acids changes from maternal tissue accretion in early-gestation to fetal, conceptus, and mammary tissue development in late-gestation. This thesis reports the method development associated with simultaneous measurements of energy and protein metabolism and its application to determine dietary lysine requirements in non-pregnant and pregnant sows using the indicator amino acid oxidation method. Two indirect calorimetry systems and an experimental feeding regimen were tested and validated for use in studies of amino acid requirements by stable isotope dilution. Protein and energy balance studies were performed in non-pregnant sows fed two distinct levels of energy and protein intake. The systems reacted appropriately to changes in gas concentrations induced by sow respiration. Protein and energy balance studies were also performed in pregnant and lactating sows fed typical diets. Sows appeared more anabolic during mid-gestation and were catabolic by late-gestation and through lactation, where additional energy intake provided by ad libitum feed intake increased milk energy output. The dietary lysine requirement in non-pregnant sows at maintenance was determined as 49 mg/kg0.75, 30% greater than current recommendations. The dietary lysine requirement was determined to be 10.1 g/d and 16.5 g/d, in early- and late-gestation, respectively. These results suggest that a constant diet formulation for the entirety of gestation is not appropriate. In conclusion, simultaneous measurements of energy and protein metabolism combining indirect calorimetry and stable isotope techniques may be used to define requirements for dietary amino acids in sows. Basic assumptions of the factorial approach to estimate requirements require further investigation, including the dietary lysine requirement. Application of phase feeding for sows during gestation can more correctly meet the demands for amino acids and energy, improving sow longevity. / Animal Science

Grb2, a modular protein comprised of a central SH2 domain flanked between a N-terminal SH3 (nSH3) domain and a C-terminal SH3 (cSH3) domain, is a component of cell signaling networks involved in the transmission of extracellular information in the form of growth factors and cytokines to downstream targets such as transcription factors within the nucleus. The Grb2-Sos1 interaction is mediated through the combinatorial binding of nSH3 and cSH3 domains of Grb2 to various sites - designated S1, S2, S3, and S4 - containing PXpsiPXR motifs within Sos1. Here, using a diverse array of biophysical techniques, including in particular isothermal titration calorimetry coupled with molecular modeling and semi-empirical analysis, I provide new insights into the Grb2-Sos1 interaction in thermodynamic and structural terms. My data show that Grb2 exists in monomer-dimer equilibrium in solution and that the dissociation of dimer into monomers is entropically-driven. The heat capacity change observed was much smaller than that expected from the rather large molecular surfaces becoming solvent-occluded upon dimerization, implying that monomers undergo conformational rearrangement upon dimerization. 3D structural models suggest strongly that such conformational rearrangement may arise from domain swapping. I further show that the nSH3 domain of Grb2 binds to the S1 site containing the proline-rich consensus motif PXpsiPXR with an affinity that is nearly three-fold greater than that observed for the binding of the cSH3 domain. It is also demonstrated that such differential binding of the nSH3 domain relative to the cSH3 domain is largely due to the requirement of a specific acidic residue, in the RT loop, to engage in the formation of a salt bridge with the arginine residue in the consensus motif PXpsiPXR. The data further reveal that, while binding of both SH3 domains to Sos1 is under enthalpic control, the nSH3 binding suffers from entropic penalty in contrast to entropic gain accompanying the binding of cSH3, implying that the two domains employ differential thermodynamic mechanisms for Sos1 recognition. Additionally, my data reveal that while the nSH3 domain of Grb2 binds with affinities in the physiological range to all four sites S1-S4, the cSH3 domain can only do so at the S1 site. Further scrutiny of these sites yields rationale for the recognition of various PXpsiPXR motifs by the SH3 domains in a discriminate manner. Unlike the PXpsiPXR motifs at S2, S3 and S4 sites, the PXpsiPXR motif at S1 site is flanked at its C-terminus with two additional arginine residues that are absolutely required for high-affinity binding of the cSH3 domain. In contrast, these two additional arginine residues augment the binding of the nSH3 domain to the S1 site but their role is not critical for the recognition of S2, S3 and S4 sites. Molecular modeling is employed to rationalize my new findings in structural terms. Taken together, this thesis provides novel insights into the physicochemical basis of a key protein-protein interaction pertinent to cellular signaling and cancer. My studies bear the potential for the development of novel therapies with less toxicity but more effectiveness for the treatment of disease.

Jun and Fos are components of the AP1 family of transcription factors that bind to the promoters of a diverse multitude of genes involved in critical cellular responses such as cell growth and proliferation, cell cycle regulation, embryonic development and cancer. The specific protein-DNA interactions are driven by the binding of basic zipper (bZIP) domains of Jun and Fos to TPA response element (TRE) and cAMP response element (CRE) within the promoters of target genes. Here, using a diverse array of biophysical techniques, including in particular isothermal titration calorimetry in conjunction with molecular modeling and semi-empirical analysis, I characterize AP1-DNA interactions in thermodynamic and structural terms. My data show that the binding of bZIP domains of Jun-Fos heterodimer to TRE and CRE are under enthalpic control accompanied by entropic penalty at physiological temperatures. This is in agreement with the notion that protein-DNA interactions are largely driven by electrostatic interactions and intermolecular hydrogen bonding. A larger than expected heat capacity change suggests that the basic regions within the bZIP domains are unstructured in the absence of DNA and interact in a coupled folding and binding manner. Further analysis demonstrates that Jun-Fos heterodimer can tolerate single nucleotide variants of the TRE consensus sequence and binds in the biologically relevant micromolar to submicromolar range. Of particular interest is the observation that the Jun-Fos heterodimer binds to specific variants in a preferred orientation. 3D atomic models reveal that such preference in orientation results from asymmetric binding and may in part be attributable to chemically distinct but structurally equivalent residues within the basic regions of Jun and Fos. I further demonstrate that binding of the biologically relevant Jun-Jun homodimer to TRE and CRE occurs with favorable enthalpic contributions accompanied by entropic penalty at physiological temperatures in a manner akin to the binding of Jun-Fos heterodimer. However, anomalously large negative heat capacity changes provoke a model whereby Jun loads onto DNA as unfolded monomers coupled with subsequent folding and homodimerization upon association. The data also reveal that the heterodimerization of leucine zippers is modulated by the basic regions and these regions may undergo at least partial folding upon heterodimerization. Large negative heat capacity changes accompanying the heterodimerization of leucine zippers are consistent with the view that leucine zippers do not retain a-helical conformation in isolation and the formation of the native coiled coil a-helical dimer is attained through a coupled folding-dimerization mechanism. Taken together, this dissertation marks the first comprehensive thermodynamic analysis of an otherwise well-studied and vitally important transcription factor. My studies shed new light on the forces driving the AP1-DNA interaction in thermodynamic and structural terms. The implications of these novel findings on the development of novel therapies for the treatment of disease with greater efficacy coupled with low toxicity cannot be overemphasized.

Following several terrorist attacks that have occurred during this decade, there is an urgent need to develop new technologies for the detection of highly energetic materials that can represent an explosive hazard. In an effort to contribute to the development of these new technologies, this work presents the design aspects of a chip-scale calorimeter that can be used to detect an explosive material by calorimetric methods. The aim of this work is to apply what has been done in the area of chip-scale calorimetry to the screening of highly energetic materials. The prototypes presented here were designed using computer assisted design and finite element analysis tools. The design parameters were set to satisfy the requirements of a sensor that can be integrated into a portable system (handheld) for field applications. The design approach consisted of developing a sensor with thick silicon membranes that can hold micro-size samples and that can operate at high temperatures, while keeping the cost of the sensor low. Contrary to other high resolution systems based on thin-film membranes, our prototypes exhibit a contribution from addenda that is comparable to that from the sample, and hence they have lower sensitivity. However, using thick membranes offers the advantage of producing sensors strong enough for this application and that have significantly lower cost. Once the prototypes were designed, the fabrication was performed using standard microfabrication techniques. Finally, the operation of our prototypes was demonstrated by conducting thermal analysis of different liquid and solid samples.

Ethylene oxide (EO) is a very versatile compound with considerable energy in its ring structure. Its reactions proceed mainly via ring opening and are highly exothermic. Under some conditions, it is known to undergo a variety of reactions, such as isomerization, polymerization, hydrolysis, combustion and decomposition Due to its very reactive characteristic and widely industrial applications, EO has been involved in a number of serious incidents such as Doe Run 1962, Freeport 1974, Deer Park 1988 and Union Carbide Corporation’s Seadrift 1991. The impacts can be severe in terms of death and injury to people, damage to physical property and effects on the environment. For instance, the Union Carbide incident in 1991 caused one fatality and extensive damage to the plant with the property damage of up to 80 million dollars. Contamination has a considerable impact on EO reactivity by accelerating substantially its decomposition and playing a key role on EO incidents. In this work, the reactivity of EO with contaminants such as KOH, NaOH, NH4OH, and EDTA is evaluated. Useful information that is critical to the design and operation of safer chemical plant processes was generated such as safe storage temperatures (onset temperature), maximum temperature, maximum pressure, temperature vs. time, heat and pressure generation rates as a function of temperature and time to maximum rate using adiabatic calorimetry. A special arrangement for the filling-up of the cell was constructed due to the gaseous nature and toxicity of EO. A comparison of their thermal behavior is also presented since several contaminants are studied.

Calcium aluminate cement (CAC) is a rapid hardening cementitious material often used in niche concrete repairs where high early-age strength and robust durability are required. This research project characterized the implications of the additions of various mineral and chemical admixtures to plain CAC to mitigate strength reductions associated with conversion, an inevitable strength reduction associated with the densification of metastable hydrates (CAH10 and C2AH8) to stable hydrates (C3AH6 and AH3). The effect of these admixtures on early-age strength development, volume change, and the correlation to macro-scale performance were reported in this dissertation. Various mixtures of CAC were investigated including: pure CAC, binary blends of CAC with fly ash (Class C) or CaCO3, and ternary blends of CAC with slag and silica fume. Characterization of the influence of these admixtures on hydration was completed using x-ray diffraction, isothermal calorimetry, and chemical shrinkage. Investigations on the implications of early-age volume change were conducted for autogenous deformation. In addition to laboratory testing, the final phase of the project was to correlate and elucidate the data generated in the laboratory to real-world field performance. Field trials were conducted to evaluate and monitor the behavior of CAC systems and investigate the link between laboratory generated research and actual large scale behavior. / text

Assessing hazards due to energetic or reactive chemicals is a challenging and complicated task and has received considerable attention from industry and regulatory bodies. Thermal analysis techniques, such as Differential Scanning Calorimeter (DSC), are commonly employed to evaluate reactivity hazards. A simple classification based on energy of reaction (-H), a thermodynamic parameter, and onset temperature (To), a kinetic parameter, is proposed with the aim of recognizing more hazardous compositions. The utility of other DSC parameters in predicting explosive properties is discussed. Calorimetric measurements to determine reactivity can be resource consuming, so computational methods to predict reactivity hazards present an attractive option. Molecular modeling techniques were employed to gain information at the molecular scale to predict calorimetric data. Molecular descriptors, calculated at density functional level of theory, were correlated with DSC data for mono nitro compounds applying Quantitative Structure Property Relationships (QSPR) and yielded reasonable predictions. Such correlations can be incorporated into a software program for apriori prediction of potential reactivity hazards. Estimations of potential hazards can greatly help to focus attention on more hazardous substances, such as hydroxylamine (HA), which was involved in two major industrial incidents in the past four years. A detailed discussion of HA investigation is presented.