In modern separation design, an important part of many phase-equilibrium calculations is the mathematical representation of pure-component and mixture enthalpies. Mixture enthalpy data are important not only for determination of heat loads, but also for the design of distillation units. Further, mixture enthalpy data, when available, are useful for extending vapor-liquid equilibria to higher (or lower) temperatures, through the use of the Gibbs-Helmholtz equation. In this connection excess molar enthalpies for several binary and ternary mixtures involving ethers and hydrocarbons have been measured at the temperature 298.15 K and atmospheric pressure, over the whole mole fraction range. Values of the excess molar enthalpies were measured by means of a modified flow microcalorimeter (LKB 10700-1) and the systems show endothermic behavior. The Redlich-Kister equation has been used to correlate experimental excess molar enthalpy data of binary mixtures. Smooth representations of the excess molar enthalpy values of ternary mixtures are accomplished by means of the Tsao-Smith equation with an added ternary contribution term and are used to construct excess enthalpy contours on Roozeboom diagrams. The values of the standard deviations indicate good agreement between experimental results and those calculated from the smoothing equations. The experimental excess enthalpy data are also correlated and predicted by means of solution theories (Flory theory and Liebermann-Fried model) for binary and ternary mixtures, respectively. These solution theories correlate the binary heats of mixing data with reasonable accuracy. The prediction of ternary excess molar enthalpy by means of the solution theories are also presented on Roozeboom diagrams. The predictions of ternary excess enthalpy data by means of these theories are reasonably reliable.

SHAPE-DEPENDENT MOLECULAR RECOGNITION OF SPECIFIC SEQUENCES OF DNA BY HETEROCYCLIC CATIONS by YI MIAO Under the Direction of Dr. W. David Wilson ABSTRACT DB921 and DB911 are biphenyl-benzimidazole-diamidine isomers with a central para- and meta-substituted phenyl group, respectively. Unexpectedly, linear DB921 has much stronger binding affinity with DNA than its curved isomer, DB911. This is quite surprising and intriguing since DB911 has the classical curved shape generally required for strong minor groove binding while DB921 clearly does not match the groove shape. Several biophysical techniques including thermal melting (Tm), circular dichroism (CD), biosensor-surface plasmon resonance (SPR), and isothermal titration calorimetry (ITC) have been utilized to investigate the interactions between these compounds and DNA. The structure of the DB921-DNA complex reveals that DB921 binds to DNA with a reduced twist of the biphenyl for better fit of DB921 into the minor groove. A bound water molecule complements the curvature of DB921 and contributes for tight binding by forming H-bonds with both DNA and DB921. Structure-affinity relationship studies of a series of DB921 analogs show that the benzimidazole group is one of the key groups of DB921 for its strong binding to the minor groove. Thermodynamic studies show that the stronger binding of DB921 is due to a more favorable binding enthalpy compared to DB911 even though the complex formation with DNA for these compounds are all predominantly entropically driven. DB921 also has more negative heat capacity change than DB911. The initial studies of inhibition of the interaction between an AT hook peptide of HMGA proteins and its target DNA by a set of diamidine AT-minor groove binders using biosensor-SPR technique show that the inhibitory ranking order is consistent with that of binding affinity and linear-shaped DB921 still has excellent inhibitory effects. These heterocyclic cations rapidly inhibit the binding of DBD2 peptide to the DNA and may only block the specific AT binding of the peptide without hindering the non-specific binding interaction. The results of this project have shown that DB921 represents a new novel effective minor groove binder that does not fit the traditional model and is a potential inhibitor for DNA/protein complexes. INDEX WORDS: Molecular recognition, DNA binding, Minor groove binding, Linear shape, Compound curvature, Binding affinity, Binding kinetics, Thermodynamics, Surface plasmon resonance, Isothermal titration calorimetry, Inhibition

In modern separation design, an important part of many phase-equilibrium calculations is the mathematical representation of pure-component and mixture enthalpies. Mixture enthalpy data are important not only for determination of heat loads, but also for the design of distillation units. Further, mixture enthalpy data, when available, are useful for extending vapor-liquid equilibria to higher (or lower) temperatures, through the use of the Gibbs-Helmholtz equation. In this connection excess molar enthalpies for several binary and ternary mixtures involving ethers and hydrocarbons have been measured at the temperature 298.15 K and atmospheric pressure, over the whole mole fraction range. Values of the excess molar enthalpies were measured by means of a modified flow microcalorimeter (LKB 10700-1) and the systems show endothermic behavior. The Redlich-Kister equation has been used to correlate experimental excess molar enthalpy data of binary mixtures. Smooth representations of the excess molar enthalpy values of ternary mixtures are accomplished by means of the Tsao-Smith equation with an added ternary contribution term and are used to construct excess enthalpy contours on Roozeboom diagrams. The values of the standard deviations indicate good agreement between experimental results and those calculated from the smoothing equations. The experimental excess enthalpy data are also correlated and predicted by means of solution theories (Flory theory and Liebermann-Fried model) for binary and ternary mixtures, respectively. These solution theories correlate the binary heats of mixing data with reasonable accuracy. The prediction of ternary excess molar enthalpy by means of the solution theories are also presented on Roozeboom diagrams. The predictions of ternary excess enthalpy data by means of these theories are reasonably reliable.

Metallic glasses can be considered for many commercial applications because of the higher mechanical strength, corrosion and wear resistance when compared to crystalline materials. To consider them for novel applications, the challenge of preparing metallic glasses from the liquid melt phase and how the properties of metallic glasses change due to relaxation need to be understood better. The glass forming ability (GFA) with variation in composition and inclusion of different alloying elements was studied by using thermal techniques to determine important GFA indicators for Zr-based bulk metallic glasses (BMG). The effect of alloying elements, annealing temperature and annealing time on the thermal and structural relaxation of the BMGs was studied by using an annealing induced relaxation approach. The thermal relaxation was studied by measuring specific heat of the samples using differential scanning calorimeter (DSC) and calculating the enthalpy recovery on reheating in the BMG samples. The structural relaxation was also studied by using extended X-ray absorption fine structure (EXAFS) technique on the as-obtained and relaxed samples. The effects of alloying elements and annealing on electrical resistance were studied by using a two point probe. From the study, it was found that the currently used GFA indicators are inadequate to fully capture and identify the best GFA BMGs. The fragility (beta) of the melt is a new criterion that has been proposed to measure and analyze GFA. The enthalpy relaxation of Zrbased BMGs was found to follow a stretched exponential function, and the parameters obtained showed the BMGs used in the current study are strong glass formers. EXAFS studies showed variations in the structure of BMGs with changes in alloying elements. Furthermore, alloying elements were found to have an effect on the structure of the relaxed BMGs. The resistance of BMGs was found to decrease with relaxation which can be attributed to short range order on annealing.

Baigiamojo darbo tikslas – nustatyti paviršinio aktyvumo medžiagų micelių susidarymo koncentracijas ir įvertinti tirpalų rūgštinių-bazinių savybių pokyčius paviršinio aktyvumo medžiagų ir rūgštinių dažiklių vandeniniuose tirpaluose. Kritinė micelių susidarymo koncentracija nustatyta atlikus tirpalų elektrinio laidumo ir šviesos absorbcijos matavimus, naudojantis konduktometriniu bei spektrofotometriniu tyrimo metodais. Dažiklių rūgštinių-bazinių savybių kitimas vandeniniuose tirpaluose įvertintas nustačius dažiklio disociacijos konstantų neigiamo logaritmo vertes ir termodinaminius parametrus. Paviršinio aktyvumo medžiagų, tokių kaip natrio dodecilsulfato, dodeciltrimetilamonio chlorido ir joninio tirpalo 1-dodecil-3-metilimidazolio chlorido kritinės micelių susidarymo koncentracijos buvo nustatytos Žaliojo B dažiklio vandeniniuose bei buferiniuose tirpaluose. Nustatyta, kad paviršinio aktyvumo savybe pasižyminčių medžiagų kritinės micelių susidarymo koncentracijų vertės priklauso nuo tirpalo pH, o didinant tirpalo joninę jėgą jos mažėja. Rūgštinio Oranžinio 7 ir Rūgštinio Mėlynojo 80 dažiklių disociacijos konstantų neigiamo logaritmo pKr vertės kito priklausomai nuo vandeninio tirpalo temperatūros, pH vertės ir naudotų skirtingos prigimties paviršinio aktyvumo medžiagų. Nustatyta, kad Rūgštinio Oranžinio 7 dažiklio rūgštinės savybės stipriausiai išreikštos, kai tirpale buvo amfoterinės paviršinio aktyvumo medžiagos – kokoamidopropilbetaino, o Rūgštinio Mėlynojo 80 -... [toliau žr. visą tekstą] / The aim of this work was to determinate the critical micelle concentration of surfactants and to evaluate the variation of acidic-basic properties of acidic dyes and surfactants solutions. The critical micelle concentration was determinated by the measurements of electrical conductivity and absorption, using electrical conductivity and UV-vis absorption spectrometry methods. The variation of acidic-basic properties of dyes in aqueous solutions was evaluated by estimation the values of the negative logarithm of dissociation constant of the dye and thermodynamic parameters of dyes-surfactants solution. The critical micelle concentration of sodium dodecyl sulfate, dodecyltrimethylammonium chloride and 1-dodecyl-3-methylimidazolium chloride was determinated in aqueous and phosphate buffered solutions of the Janus Green B dye. The value of critical micelle concentration of anionic, cationic surfactants and ionic compound depends on the pH value of the solutions, it can be observed that increasing the ionic strength of solution the value of critical micelle concentration decreases. The values of the negative logarithm of dissociation constant of Acid Orange 7 and Acid Blue 80 dyes varied depending on the temperature of aqueous solution, the pH value and the nature of used surfactants. It was estimated, that the lowest value of pKa of Acid Orange 7 dye was then the amphoteric surfactant - cocamidopropyl betaine was used in the dye solution and for Acid Blue 80 dye – nonionic... [to full text]

The heat capacity and the enthalpy of crystallization of the crystalline phases at the end of cooling must be known in order to determine the excess energy of mixing two pure triglycerides, trilaurin and trimyristin, cooled at different cooling rates. The present investigation was carried out using Differential Scanning Calorimetry, DSC, Modulated Differential Scanning Calorimetry, MDSC®, and Thermal Relaxation (in a Physical Properties Measurement System, PPMS). It was found that enthalpy of crystallization values can be measured to within ? 2% (SE) with DSC Q100 TA Instruments. To achieve this, an experimental procedure and a data analysis method are proposed. It was not possible in this study to obtain accurate and reproducible heat capacity values using a DSC Q100 instrument. The values were shown to be significantly by the position of the sample pan in the measuring sensor. PPMS Cp values were within the literature values.

No description available.

Air-to-air energy recovery wheels are now widely used in industry and buildings; however, the effectiveness of water vapor exchange in these regenerative wheels appears to be much lower than may be economically feasible. The purpose of this research is to investigate the feasibility of using agglomerated desiccant particle coatings to improve the performance of regenerative wheels used in HVAC air-to-air heat and moisture exchange and energy recovery applications. Desiccant particles coated on wheels lose most of their water vapor sorption capacity due to the method of coating. Desiccant agglomerates can be made by mixing starch, fine silica gel particulate, and water within an agglomerating device. The desiccant particle agglomerating process improves the desiccant mass transfer properties by increasing the overall surface area of desiccant particles; and also by creating a much rougher surface that can increase the likelihood of turbulent flow, and therefore, increasing the overall mass transfer rates. The industrial desiccant coating process involves submerging the desiccant into a coating agent and then applying this mix to the substrate or the matrix of the energy wheel. This process was improved in this research by ensuring the particles are applied after the coating agent is applied to ensure that the agglomerates or desiccant particles are not submerged by the coating material. Because testing energy wheels under steady state operating conditions has proved to be difficult, time consuming and costly in the past, a small parallel flow test cell is used to measure the transient response of coated substrate aluminum sheets after a step change in the inlet air humidity or temperature. Using a previously developed theoretical model, the time constants for these inlet step change responses are then used to predict the sensible and latent effectiveness of a regenerative energy wheel coated with the same agglomerated particles, which is rotated at a known operating speed and wheel face velocity. When the new desiccant coatings are used, it is shown that the latent heat effectiveness for a typical wheel could be up to 85%. It is found that the steady state air flow pressure drop readings for the test cell shows that agglomerated particles coated on the surfaces within the test cell implies some transitional turbulent flow behavior compared to similar substrate surfaces coated in a conventional manner with desiccant particles (e.g. up to 60% higher pressure drop at a channel Reynolds number of 300) in the same test cell. This implied enhanced turbulence flow friction factor in the test cell suggests a somewhat similar enhancement for increased mass and heat transfer coefficients for the test cell or coated wheel matrices. The transient results for humidity step changes for air flow through the test cell reveals that the adsorption and desorption response time constants are much larger for the agglomerated coated substrate surfaces than the conventional industrial coated surfaces. These data imply much higher moisture or latent heat effectiveness values for wheels coated with agglomerated particles. When the new desiccant coatings are used, it is shown that the latent heat effectiveness for a typical wheel could be better than 80% or 20% higher than currently available typical energy wheels. With improvements to the desiccant particle agglomerating process, desiccant coating process and particle coating and testing methods, this thesis shows that significant improvements may be practical for the design, testing and operation of regenerative heat and moisture exchange wheels.

Thesis (M.S.); Submitted to Iowa State Univ., Ames, IA (US); 12 Dec 2003. / Published through the Information Bridge: DOE Scientific and Technical Information. "IS-T 2547" Elizabeth M. Lenihan. 12/12/2003. Report is also available in paper and microfiche from NTIS.

Thesis (M.S.)--Brigham Young University. Dept. of Chemical Engineering, 2005. / Includes bibliographical references (leaves 89-95).