PROLINE-BASED CHIRAL STATIONARY PHASES: INSIGHTS INTO THE MECHANISM OF CHIRAL SELECTIVITY

Proline (Pro) is a unique amino acid that has been examined previously as a potential chiral selector for high-performance liquid chromatography. In recent years, a new class of promising Pro based enantioselective stationary phases has been studied and the longer peptides were found to be competitive with commercial chiral stationary phases (CSPs). Here, we aim to perform a comprehensive examination of a t-butoxycarbonyl- (t-Boc-) terminated monoproline selector. This selector was grafted through an amide linkage to an aminopropyl siloxane-terminated Si (111) wafer and to a silicon atomic force microscopy tip. To ensure a flat, homogeneous overlayer of selectors suitable for force spectrometric measurements, the prepared surfaces were characterized using XPS, AFM and contact angle measurements. Chemical force spectrometry (CFS) has been used to examine the chiral discrimination in our monoproline CSP by measuring the interaction forces between two D- or L-monoproline monolayers in water and in the presence of a series of amino acids in solution to explore the degree to which binding of amino acids impacts self-selectivity. Chemical force titration (CFT) has been used to observe the influence of variations in pH on the binding interaction of proline modified chiral surfaces. Here we aim to explore the connection between side-chain hydrophobicity and differences in the nature of the binding between different ionic forms of amino acids and the t-Boc-Pro interface, and thereby to gain insight into the mechanism of chiral selectivity. The CFS results show several trends for different proline selector/amino acid combinations and indicate that the binding characteristics of amino acid to the proline surface is strongly dependent on the amino acid side chain where hydrophilic side chain amino acids exhibit a selectivity opposite to that seen for those with hydrophobic side chains. The CFT studies also provide valuable insights into interactions between the proline selector and the amino acids under a wide range of pH conditions, indicating that protonated amine groups of alanine and serine are closely involved in the binding mechanism to proline surfaces. On the other hand, the presence of the second carboxylic group in aspartic acid plays an important role while interacting with proline.

Sandcastles of hope? Civil society organizations and the working conditions of migrant farmworkers in North America

This research explores whether civil society organizations (CSOs) can contribute to more effectively regulating the working conditions of temporary migrant farmworkers in North America. This dissertation unfolds in five parts. The first part of the dissertation sets out the background context. The context includes the political economy of agriculture and temporary migrant labour more broadly. It also includes the political economy of the legal regulations that govern immigration and work relations. The second part of the research builds an analytical model for studying the operation of CSOs active in working with the migrant farmworker population. The purpose of the analytical framework is to make sense of real-world examples by providing categories for analysis and a means to get at the channels of influence that CSOs utilize to achieve their aims. To this end, the model incorporates the insights from three significant bodies of literature—regulatory studies, labour studies, and economic sociology. The third part of the dissertation suggests some key strategic issues that CSOs should consider when intervening to assist migrant farmworkers, and also proposes a series of hypotheses about how CSOs can participate in the regulatory process. The fourth part probes and extends these hypotheses by empirically investigating the operation of three CSOs that are currently active in assisting migrant farm workers in North America: the Agricultural Workers Alliance (Canada), Global Workers’ Justice Alliance (USA), and the Coalition of Immokalee Workers (USA). The fifth and final part draws together lessons from the empirical work and concluded that CSOs can fill gaps left by the waning power of actors, such as trade unions and labour inspectorates, as well as act in ways that these traditional actors can not.