In chapter 1 the principles behind circular dichroism spectroscopy and exciton coupled circular dichroism spectroscopy are outlined, and examples are cited that illustrate the utility of these methods in the determination of absolute configuration and ee of chiral amines. This provides background and context for this thesis, which mostly pertains to the sensing of chirality in amines. An exciton coupled circular dichroism method based on the induction of helical chirality in an organometallic host for sensing chiral amines is presented in chapter 2. The method can be used to determine absolute configuration by relating the sign of the first Cotton effect of the host-amine complex to the handedness of the amine. Analysis of the primary circular dichroism optical data is by principal component analysis allows for differentiation of the analytes based on their idendity and handedness. A novel circular dichroism method for detecting chiral amines is discussed in chapter 3. The method uses a highly efficient derivatization method to convert the primary amine into a bidentate imine. Three equivalents of the imine are then assembled together by coordination to Fe(II). The proximity and chiral orientation of the imines leads to exciton coupled circular dichroism, which is of utility in the determination of absolute configuration. Additionally, there is a metal-to-ligand charge transfer band in the visible region that can be used to develop calibration curves, which allow for the determination of the enantiomeric excess of unknown samples with an absolute error of ±5%. Chapter 4 details another imine based circular dichroism method for chiral amines. The method uses a commercially available aldehyde, Fe(II), and circular dichroism spectrometry to sense chirality in amines. It is shown that the circular dichroism signals in the ultraviolet spectrum vary predictably with the handedness of the chiral amine, which has potential applications in the determination of absolute configuration. By developing calibraton curves, signals in the visible spectrum can be used to determine enantiomeric excess with an absolute error of ±6%. Analyzing the primary circular dichroism optical data with linear discriminant analysis allows for differentiation between amines based on their identity and handedness. Finally, chapter 5 illustrates the potential of using the thermodynamic parameters of partitioning between water and octanol as a predictive tool for estimating the contributions of hydrophobicity to host-guest binding events. This is done by showing a relationship between the thermodynamics of partitioning and thermodynamics of hydrophobic binding events for a series of guests and cyclodextrin. A plot of the thermodynamic parameters of binding of a variety of guests to cyclodextrin as a function of the thermodynamic parameters of partitioning between water and octanol shows a linear relationship for a series of alcohols. / text

Sensing in scattering environments, such as fog and dust, poses a serious challenge for all optical systems and is important for many critical surveillance applications. The use of polarized light, specifically circularly polarized light, has shown great promise for improving detection range and sensing in highly scattering, real-world environments. While the potential impact to application is significant, the optical science and sensing community lacks data on broad wavelength and environmental parameters where circularly polarized light outperforms linearly polarized light, increasing detection range and signal persistence. In this dissertation I quantify, through simulation and experimental results, the advantage of circularly polarized light in laboratory and real-world scattering environments - focusing on circularly polarized light's superior persistence in these environments. I present new and unique contributions to the study of polarized light in both isotropic (Rayleigh regime) and forward-scattering environments, showing circular polarization's superior persistence increases detection range for real-world environments over broad wavelength and particle size regimes. Utilizing polarization-tracking Monte Carlo simulations for varying particle size, wavelength, and refractive index, I quantify when circular polarization outperforms linear polarization in maintaining the illuminating polarization state for large optical thicknesses, persisting to longer ranges. I identify many real-world environments with particle sizes of radiation fog, advection fog, and Sahara dust where circular polarization outperforms linear polarization over broad wavelength ranges in the infrared spectrum. This enhancement with circular polarization can be exploited to improve sensing range and target detection in obscurant environments that are important in many critical surveillance applications. Conversely, I also identify a few environmental configurations where linear polarization outperforms circular polarization. However, circular polarization's response is generally larger and over broader wavelength ranges in the infrared regime for real-world scattering environments. Experiments were conducted for both 1) isotopically-scattering (Rayleigh regime) environments and 2) forward-scattering environments using polystyrene microspheres with well-defined diameters. These measurements demonstrated that in the forward-scattering environments, circular polarization persists through increasing optical thickness better than linear polarization. Variations in persistence were investigated as a function of collection geometry, angular field of view, and collection area. Persistence for both linear and circular polarization was found to be more susceptible to collection geometry, specifically increased collection area, in the isotropically-scattering (Rayleigh regime) environment. Similarly, linear polarization in the forward-scattering environments is dependent upon changes in collection geometry. Significantly, circular polarization's response is nearly unaffected by variations of both field of view and collection area for the forward-scattering environments. Circular polarization proves to be not only generally better in persistence but also more tolerant of variations in angular collection and collection area compared to linear polarization, making it ideal and flexible for use in optical sensing systems in scattering environments. Finally, I present simulation results that show the evolution of linear and circularly polarized light as it scatters throughout both isotropic (Rayleigh regime) and forward-scattering environments as a function of scattering event. Circularly polarized light persists through a larger number of scattering events longer than linearly polarized light for all forward-scattering environments; but not for scattering in the Rayleigh regime. Circular polarization's increased persistence occurs for both forward and backscattered light. The evolution of the polarization states as they propagate through the various environments are illustrated on the Poincaré sphere after successive scattering events. This work displays individual scattering events as well as a cumulative, measureable result, in an intuitive manner. Throughout this dissertation I quantify the polarization persistence and memory of circularly polarized light in real-world scattering environments over broad wavelength, particle size, and collection-geometry parameter spaces; and for the first time, detail the evolution and modification of both circularly and linearly polarized states through isotropic and forward-scattering environments. These results show how circular polarization can extend range and sensing capability in surveillance sensing applications in real-world scattering environments.

To understand protein stability and the mechanism of protein folding, it is essential that we gain a better understanding of the ensemble of conformations that make up the denatured state of a protein. The primary goal of the research described here was to see what we might learn about the denatured state using fluorescence. To this end, tryptophan was introduced at five sites in Ribonuclease Sa (RNase Sa): D1W, Y52W, Y55W, T76W, and Y81W. The fluorescent properties of the denatured states of these five proteins were studied and compared to the fluorescent properties of eight model compounds: N-acetyl-tryptophan-amide (NATA), N-acetyl-Ala-Trp-Ala-amide (AWA), N-acetyl-Ala-Ala-Trp-Ala-Ala-amide (AAWAA), and five pentapeptides based on the sequence around the original tryptophan substitutions in RNase Sa. Regardless of the denaturant, λmax for the proteins and model compounds differed very little, 349.3 ± 1.2 nm. However, significant differences were observed in the fluorescence intensity at λmax (IF), suggesting that IF is more sensitive to the immediate environment than λmax. The differences in IF are due in part to quenching by neighboring side chains. More importantly, IF was always significantly greater in the protein than in its corresponding pentapeptide, indicating that the protein exerts an effect on the tryptophan, which cannot be mimicked by the pentapeptide models. Acrylamide and iodide quenching experiments were also performed on the model compounds and proteins. Significant differences in the Stern-Volmer quenching constant (KSV) were also observed between the proteins and between the proteins and their corresponding pentapeptides. Importantly, the KSV for the protein was always less than in its corresponding pentapeptide. These data along with the IF data show that non-local structure in the unfolded state influences tryptophan fluorescence and accessibility. In summary, these and our other studies show that fluorescence can be used to gain a better understanding of the denatured states of proteins.

A polymer photodetector is fabricated using polythiophene with chiral alkyl side chains. The Cotton effect is observed in the CD spectrum of the photodetector, indicating an unequal absorbance of left- and right-handed circular polarized light (CPL). The photodetector is proven to be able to identify incident left- and right-handed CPL. Polymer photodetectors that are made from R- and S-limonene induced achiral polymers are fabricated. A “hot spin-coating” process is introduced to cast uniform limonene induced polymer films. As a result of chirality transfer, Cotton effects are also observed in these photodetectors’ CD spectra. A model is suggested to explain the chirality generation of the polythiophene with chiral alkyl side chains and limonene induced achiral polymers. / Thesis (Master, Chemistry) -- Queen's University, 2014-03-25 14:37:23.168

En el curso de esta Tesis Doctoral, se sintetizaron librerías de (1,2)-diaminas enantiopuras y 2,2’-bifenoles pro-quirales. La transferencia de quiralidad desde la diamina al bifenol, mediante puentes de hidrógeno o coordinación a un metal (ZnII, CuII), fue demostrada por dicroísmo circular (DC). El comportamiento en disolución de los complejos supramoleculares (usando puentes de hidrógeno), así como sus constantes de asociación, fue estudiado mediante valoraciones de RMN, UV-vis y ITC. La determinación de las configuraciones absolutas de los complejos de ZnII se consiguió mediante la resolución de las estructuras de rayos-X y los estudios de DC, tanto a un nivel teórico como experimental. Un nuevo ligando fosforado, potencialmente catalítico, fue preparado a partir de 2,2’-bifenol, mostrando el camino para el desarrollo de nuevos catalizadores supramoleculares. / During the course of the thesis libraries of chiral (1,2)-diamines and prochiral 2,2’-biphenol derivatives were synthesised. The transfer of chirality from the diamine to the biphenol moiety mediated either by hydrogen bonding or coordination to a metal centre (ZnII, CuII) was demonstrated by CD (circular dicroism). The behaviour in solution of the hydrogen bonded complexes was investigated by NMR spectroscopy, UV-vis and ITC titrations (determination of association constants. The determination of absolute configurations of the ZnII complexes was achieved by X-ray structure determination and CD analyses both on the experimental and theoretical level. Last but not least, a new potentially catalytic phosphane ligand was derived from a dynamically racemic 2,2’-biphenol derivative.

No description available.

Tat1-72, is an intrinsically disordered protein at pH 4.1 as previously indicated by NMR chemical shifts and coupling constants, and confirmed by 15N-relaxation parameters. The presence of SDS elicits a conformational change to α-helicity in Tat1-72. In the presence of the non-ionic DDM detergent and zinc, Tat was found to be soluble at pH 4 when bound to TAR RNA; TAR binding also elicits a conformational shift to α-helicity in Tat1-72. The β-sheet content of Tat1-72 is increased in the presence of NaCl. In similar conditions, Tat1-72 aggregates stained with Congo Red displayed a yellow-green birefringence and a red-shift in the Congo Red absorbance that is typical of β-amyloid fibril. The web-based algorithm “WALTZ” identifies the majority of the Tat1-72 hydrophobic core region as amyloidogenic. The helical propensity of Tat1-72 in TFE was determined by two-dimensional NMR spectroscopy.

No description available.

The aim of this study is to analyze how the concept of circular economy is viewed and defined within the Swedish public sector. Discourse analysis was applied to the semi-structured interviews conducted with employees who work with circular economy projects at local, regional and national institutions. The research found that circular economy was perceived as a way to face resource limitations through continuous circulation of materials, which could also foster economic growth decoupled from extraction of finite resource. Actors perceived as important for the transition to a circular economy are: public sector, business, researchers and civil society, who are believed to be motivated by the notion that a circular economy will lead to a more sustainable society. Furthermore, it is assumed that different partners will work together towards the common goal of circular economy. In addition, the circular economy concept seems to offer a different rhetorical way of approaching environmental problems. The implications of this study could be used to deepen understandings of how circular economy could be implemented.

No description available.