A comparative study of protoheme and heme d catalases : role of the heme and the heme pocket in catalysis and ligand binding

Catalase dismutes H20 2 to O2 and H20. In successive twoelectron reactions H20 2 induces both oxidation and reduction at the heme group. In the first step the protoheme prosthetic group of beef liver catalase forms compound I, in which the heme has been oxidized from Fe3+ to Fe4+=0 and a porphyrin radical has been created. Compound II is formed by the oneelectron reduction of comp I. It retains Fe4+=0 but lacks the porphyrin radical and is catalytically inert. Molecular structures are available for Escherichia coli Hydroperoxidase II, Micrococcus Iysodeiktus, Penicillium vitale and beef liver enzymes, which contain different hemes and heme pockets. In the present work, the pockets and substrate access channels of protoheme (beef liver & Micrococcus) and heme d (HPII of E. coli and Penicillium) catalases have been analysed using Quanta™ and CharmMTM molecular modeling packages on the Silicon Graphics Iris Indigo 2 computer. Experimental studies have been carried out with two catalases, HPII (and its mutants) and beef liver. Fluoride and formate' are inhibitors of both enzymes, and their binding is modulated by the heme and by distal residues N201 & H128. Both HPII and beef liver enzymes form compound I with H202 or peracetate. The reduction of beef liver enzyme compound I to II and the decay of compound II are accelerated by fluoride. The decay of compound II is also accelerated by formate, and this reagent acts as a 2-electron donor towards compound I of both enzymes. It is concluded that heme d enzymes (Penicillium and HPII of E. coli) are formed by autocatalytic transformation of protoheme in a modified pocket which contains a characteristic serine residue as well as a partially occluded heme channel. They are less active than protoheme enzymes but also do not form the inactive compound II species. Binding of peroxide as well as fluoride and formate is prevented by mutation of H128 and modulated by mutation of N201.

A dimensional analysis of the benzylic hydroxylase active site in mortierella isabellina

The spatial limits of the active site in the benzylic hydroxylase enzyme of the fungus Mortierella isabellina were investigated. Several molecular probes were used in incubation experiments to determine the acceptability of each compound by this enzyme. The yields of benzylic alcohols provided information on the acceptability of the particular compound into the active site, and the enantiomeric excess values provided information on the "fit" of acceptable substrates. Measurements of the molecular models were made using Cambridge Scientific Computing Inc. CSC Chem 3D Plus modeling program. i The dimensional limits of the aromatic binding pocket of the benzylic hydroxylase were tested using suitably substituted ethyl benzenes. Both the depth (para substituted substrates) and width (ortho and meta substituted substrates) of this region were investigated, with results demonstrating absolute spatial limits in both directions in the plane of the aromatic ring of 7.3 Angstroms for the depth and 7.1 Angstroms for the width. A minimum requirement for the height of this region has also been established at 6.2 Angstroms. The region containing the active oxygen species was also investigated, using a series of alkylphenylmethanes and fused ring systems in indan, 1,2,3,4-tetrahydronaphthalene and benzocycloheptene substrates. A maximum distance of 6.9 Angstroms (including the 1.5 Angstroms from the phenyl substituent to the active center of the heme prosthetic group of the enzyme) has been established extending directly in ii front of the aromatic binding pocket. The other dimensions in this region of the benzylic hydroxylase active site will require further investigation to establish maximum allowable values. An explanation of the stereochemical distributions in the obtained products has also been put forth that correlates well with the experimental observations.

A crisis of social democracy : organized labour and the NDP in an era of neoliberalism

The NDP was founded out of the ashes of the Co-Operative Commonwealth Federation to cooperate with the Canadian Labour Congress to become the 'political arm of organized labour' in Canada. The NDP has long claimed they are the party which represents the policy goals of organized labour in Canada: that the NDP alone will fight for trade union rights, and will fight for Canadian workers. Divergent Paths is an examination of the links between the labour movement and the ND P in an era ofneo-liberalism. Provincial NDP governments have become increasingly neoliberal in their ideological orientation, and have often proved to be no friend to the labour movement when they hold office. The Federal party has never held power, nor have they ever formed the Official Opposition. This thesis charts the progress of the federal NDP as they become more neoliberal from 1988 to 2006, and shows how this trend effects the links between the NDP and labour. Divergent Paths studies each federal election from 1988 to 2006, looking at the interactions between Labour and the NDP during these elections. Elections provide critical junctions to study discourse - party platforms, speeches, and other official documents can be used to examine discourse. Extensive newspaper searches were used to follow campaign events and policy speeches. Studying the party's discourse can be used to determine the ideological orientation of the party itself: the fact that the party's discourse has become neoliberal is a sure sign that the party itself is neoliberal. The NDP continues to drive towards the centre of the political spectrum in an attempt to gain multi-class support. The NDP seems more interested in gaining seats at any cost, rather then promoting the agenda of Labour. As the party attempts to open up to more multi-class support, Labour becomes increasingly marginalised in the party. A rift which arguably started well before the 1988 election was exacerbated during that election; labour encouraged the NDP to campaign solely on the issue of Free Trade, and the NDP did not. The 1993 election saw the rift between the two grow even further as the Federal NDP suffered major blowbacks from the actions of the Ontario NDP. The 1997 and 2000 elections saw the NDP make a deliberate move to the centre of the political spectrum which increasingly marginalised labour. In the 2004 election, Jack Layton made no attempt to move the party back to the left; and in 2006 the link between labour and the NDP was perhaps irreparably damaged when the CAW endorsed the Liberal party in a strategic voting strategy, and the CLC did not endorse the NDP. The NDP is no longer a reliable ally of organized labour. The Canadian labour movement must decide wether the NDP can be 'salvaged' or if the labour movement should end their alliance with the NDP and engage in a new political project.

Singing Nature, Dancing Buddha: Zen, Language, and the Groundlessness of Silence

This thesis presents Zen experience as aesthetic in nature. This is done through an analysis of language, a central concern for Zen Buddhism. The thesis develops two modes of language at work in Zen: representational and indexical. What these modes of language entail, the kind of relations that are developed through their use, are explored with recourse to a variety of Zen platforms: poetry, the koan, zazen, music, and suizen. In doing so, a primacy of listening is found in Zen - a listening without a listener. Given this primacy of listening, silence comes to the forefront of the investigation. An analysis of John Cage's 4'33" provides this thesis with justification of the groundlessness of silence, and the groundlessness of subjectivity. Listening allows for the abyssal subject to emerges, which in tum allows for reality to present itself outside of the constitutive function of language.

Raising Creativity: Exploring How Creativity Can be Nurtured in Educational Contexts

The question of how we can encourage creative capacities in young people has never been more relevant than it is today (Pink, 2006; Robinson as cited in TEDtalksDirector, 2007; Eisner as cited in VanderbiltUniversity, 2009). While the world is rapidly evolving, education has the great challenge of adapting to keep up. Scholars say that to meet the needs of 21st century learners, pedagogy must focus on fostering creative skills to enable students to manage in a future we cannot yet envision (Robinson as cited in TEDtalksDirector, 2007). Further, research demonstrates that creativity thrives with autonomy, support, and without judgment (Amabile, 1996; Codack [Zak], 2010; Harrington, Block, & Block, 1987; Holt, 1989; Kohn, 1993). So how well are schools doing in this regard? How do alternative models of education nurture or neglect creativity, and how can this inform teaching practice all around? In other words, ultimately, how can we nurture creativity in education? This documentary explores these questions from a scholarly art-based perspective. Artist/researcher/teacher Rebecca Zak builds on her experience in the art studio, academia, and the art classroom to investigate the various philosophies and strategies that diverse educational models implement to illuminate the possibilities for educational and paradigmatic transformation. The Raising Creativity documentary project consists of multiple parts across multiple platforms. There are five videos in the series that answer the why, who, how, what, and now what about creativity in education respectively (i.e., why is this topic important, who has spoken/written on this topic already, how will this issue be investigated this time, what was observed during the inquiry, and now what will this mean going forward?). There is also a self-reflexive blog that addresses certain aspects of the topic in greater depth (located here, on this website) and in the context of Rebecca's lived experience to complement the video format. Together, all video and blog artifacts housed on this website function as a polyptych, wherein the pieces can stand alone individually yet are intended to work together and fulfill the dissertation requirements for Rebecca's doctorate degree in education in reimagined ways.

Social Organization on the Web: How Sex workers Rights Organizations Engage in Activism and Advocacy Work Online

The purpose of this study was to examine how sex workers rights organizations use their websites as a site of activist and advocacy work and ask (i) how do various organizations conceptualize sex work on their websites, and to what extent do they incorporate an intersectional feminist perspective? (ii) what communication strategies are used by the four organizations to target audiences in the viewing public? (iii) what audiences do the four websites target? (iv) how do the four organizations discuss successes and challenges on their websites? (v) in what ways do sex worker right organizations use websites to further their goals? The websites of Maggie’s, POWER, and Stella attempt to embrace an intersectional feminist perspective of sex work, while PACE does not. The four organizations strategically use their websites to target audiences with diverse needs, specifically through advocacy efforts in educating the general public about the legitimacy of sexual labour. Additionally, to increase the use of the websites by sex workers, using social media platforms, such as Facebook and Twitter augment the untapped potential for creating action, mobilization, interaction, and dialogue on the websites.