Mirroring Enzymes: The Role of H-Bonding In HQuin-BAM Catalyzed Asymmetric Aza-Henry Reactions: A DFT Study into the Reactivity, Mechanism, and Origins of Selectivity

The exact mechanistic understanding of various organocatalytic systems in asymmetric reactions such as Henry and aza-Henry transformations is important for developing and designing new synthetic organocatalysts. The focus of this dissertation will be on the use of density functional theory (DFT) for studying the asymmetric aza-Henry reaction. The first part of the thesis is a detailed mechanistic investigation of a poorly understood chiral bis(amidine) (BAM) Brønsted acid catalyzed aza-Henry reaction between nitromethane and N-Boc phenylaldimine. The catalyst, in addition to acting as a Brønsted base, serves to simultaneously activate both the electrophile and the nucleophile through dual H-bonding during C-C bond formation and is thus essential for both reaction rate and selectivity. Analysis of the H-bonding interactions revealed that there was a strong preference for the formation of a homonuclear positive charge-assisted H-bond, which in turn governed the relative orientation of substrate binding. Attracted by this well-defined mechanistic investigation, the other important aspect of my PhD research addressed a detailed theoretical analysis accounting for the observed selectivity in diastereoselective versions of this reaction. A detailed inspection of the stereodetermining C-C bond forming transition states for monoalkylated nitronate addition to a range of electronically different aldimines, revealed that the origins of stereoselectivity were controlled by a delicate balance of different factors such as steric, orbital interactions, and the extent of distortion in the catalyst and substrates. The structural analysis of different substituted transition states established an interesting dependency on matching the shape and size of the catalyst (host molecule) and substrates (guest molecules) upon binding, both being key factors governing selectivity, in essence, offering an analogy to positive cooperative binding effect of catalytic enzymes and substrates in Nature. In addition, both intra-molecular (intra-host) and inter-molecular (host-guest, guest-guest) stabilizing interactions play a key role to the high π-facial selectivity. The application of dispersion-corrected functionals (i.e., ωB97X-D and B3LYP-D3) was essential for accurately modeling these stabilizing interactions, indicating the importance of dispersion effects in enantioselectivity. As a brief prelude to more extensive future studies, the influence of a triflate counterion on both reactivity and selectivity in this reaction was also addressed.

Simplified estimation of ray-path mirroring height for HF radiowaves reflected from the ionospheric F-region

From Milsom's equations, which describe the geometry of ray-path hops reflected from the ionospheric F-layer, algorithms for the simplified estimation of mirror-reflection height are developed. These allow for hop length and the effects of variations in underlying ionisation (via the ratio of the F2- and E-layer critical frequencies) and F2-layer peak height (via the M(3000)F2-factor). Separate algorithms are presented which are applicable to a range of signal frequencies about the FOT and to propagation at the MUF. The accuracies and complexities of the algorithms are compared with those inherent in the use of a procedure based on an equation developed by Shimazaki.

Trinity, love, and pastorial mirroring

This paper focuses on the positive mirroring (admiration, acceptance, and approval) that Heinz Kohut posits as the primary healing agency in work with clients with narcissistic personality disorder. Donald Capps has demonstrated the pastoral significance of Kohut's theory. Capps' work is extended through an analysis of the role love plays in mirroring. It is suggested that mirror love has agapic, erotic, and philial elements. The loving action of the counselor is viewed as an image of the love of the triune God.

Performance analysis of disk mirroring techniques

Unequaled improvements in processor and I/O speeds make many applications such as databases and operating systems to be increasingly I/O bound. Many schemes such as disk caching and disk mirroring have been proposed to address the problem. In this thesis we focus only on disk mirroring. In disk mirroring, a logical disk image is maintained on two physical disks allowing a single disk failure to be transparent to application programs. Although disk mirroring improves data availability and reliability, it has two major drawbacks. First, writes are expensive because both disks must be updated. Second, load balancing during failure mode operation is poor because all requests are serviced by the surviving disk. Distorted mirrors was proposed to address the write problem and interleaved declustering to address the load balancing problem. In this thesis we perform a comparative study of these two schemes under various operating modes. In addition we also study traditional mirroring to provide a common basis for comparison.

Creating a scene: Balinese punk's beginnings

The promotion of alternative music by deregulated television and recording industries, together with the increasingly felt presence of the metropolis, converged on Balinese cultural and physical landscapes in the 1990s. Mirroring developments in broader society, a regionalist discourse, which polarized notions of ‘centre’ and ‘periphery’, emerged among Balinese youth in the context of the local band scene. For certain musicians, musical authenticity was firmly rooted in a cultural and geographical locale, and was articulated by their abhorrence for socializing at shopping malls. In contrast, these Balinese alternative (including punk) musicians sought authenticity in a metropolitan elsewhere. This article is a case study of the indigenization of a ‘global’ code in a non-western periphery. It contests arguments for the ‘post-imperial’ nature of globalization, and demonstrates the continued salience of centre–periphery dialectics in local discourses. At the same time, the study attests to the progressive role a metropolitan superculture can play in cultural renewal in the periphery.

Preventing consumer credit over-commitment and irresponsible lending in Australia

Mirroring the trends in other developed countries, levels of household debt in Australia have risen markedly in recent years. As one example, the total amount lent by banks to individuals has risen from $175.5 billion in August 1995 to $590.5 billion in August 2005.1 Consumer groups an~ media commentators here have long raised concerns about the risks of increasing levels of household debt and over-commitment, linking these issues at least in part to irresponsible lending practices. And more recently, the Reserve Bank Governor has also expressed concerns about the ability 'of some households to manage if personal or economic circumstances change.2

Regulating corporate governance in China and Hong Kong : do Chinese values and ethics have a place in the age of globalization?

Much has been said about the convergence of corporate governance and regulations. The underlying assumptions of this phenomenon are driven by globalisation and the dominance of the Anglo-US model of corporate governance. Since the Asian crisis in 1997, Hong Kong and perhaps to a less extend Mainland China, had amended both Company laws and Stock Exchange Listing Rules obligations, arguably, mirroring provisions and rules in the UK and US. However, there has been a small amount of literature in law drawing from cross cultural management asking the question - is Western governance and regulation appropriate for the East? This paper will approach this issue from a different mindset, instead of drawing distinctions about East and West, a meta-regulatory framework will attempt to incorporate Western ‗hard‘ and ‗soft‘ laws with Asian ethical values. The aim is to combine laws and ethics thereby enhancing corporate governance and, improve compliance of those rules by adapting Chinese ethical values like Confucianism into the regulatory system. The overarching goal of this exercise is to adapt the wisdom of Chinese ethics into regulatory guidelines to suit the modern global market.

Hollywood dominance : will it continue?

Hollywood has dominated the global film business since the First World War. Economic formulas used by governments to assess levels of industry dominance typically measure market share to establish the degree of industry concentration. The business literature reveals that a marketing orientation strongly correlates with superior market performance and that market leaders that possess a set of six superior marketing capabilities are able to continually outperform rival firms. This paper argues that the historical evidence shows that the Hollywood Majors have consistently outperformed rival firms and rival film industries in each of those six marketing capabilities and that unless rivals develop a similarly integrated and cohesive strategic marketing management approach to the movie business and match the Major studios’ superior capabilities, then Hollywood’s dominance will continue. This paper also proposes that in cyberspace, whilst the Internet does provide a channel that democratises film distribution, the flat landscape of the world wide web means that in order to stand out from the clutter of millions of cyber-voices seeking attention, independent film companies need to possess superior strategic marketing management capabilities and develop effective e-marketing strategies to find a niche, attract a loyal online audience and prosper. However, mirroring a recent CIA report forecasting a multi-polar world economy, this paper also argues that potentially serious longer-term rivals are emerging and will increasingly take a larger slice of an expanding global box office as India, China and other major developing economies and their respective cultural channels grow and achieve economic parity with or surpass the advanced western economies. Thus, in terms of global market share over time, Hollywood’s slice of the pie will comparatively diminish in an emerging multi-polar movie business.

The dynamic processes of visual, corporate, and organisational identity : an exploratory study

The purpose of this study is to contribute to the cross-disciplinary body of literature of identity and organisational culture. This study empirically investigated the Hatch and Schultz (2002) Organisational Identity Dynamics (OID) model to look at linkages between identity, image, and organisational culture. This study used processes defined in the OID model as a theoretical frame by which to understand the relationships between actual and espoused identity manifestations across visual identity, corporate identity, and organisational identity. The linking processes of impressing, mirroring, reflecting, and expressing were discussed at three unique levels in the organisation. The overarching research question of How does the organisational identity dynamics process manifest itself in practice at different levels within an organisation? was used as a means of providing empirical understanding to the previously theoretical OID model. Case study analysis was utilised to provide exploratory data across the organisational groups of: Level A - Senior Marketing and Corporate Communications Management, Level B - Marketing and Corporate Communications Staff, and Level C - Non-Marketing Managers and Employees. Data was collected via 15 in-depth interviews with documentary analysis used as a supporting mechanism to provide triangulation in analysis. Data was analysed against the impressing, mirroring, reflecting, and expressing constructs with specific criteria developed from literature to provide a detailed analysis of each process. Conclusions revealed marked differences in the ways in which OID processes occurred across different levels with implications for the ways in which VI, CI, and OI interact to develop holistic identity across organisational levels. Implications for theory detail the need to understand and utilise cultural understanding in identity programs as well as the value in developing identity communications which represent an actual rather than an espoused position.

Good practice for enhancing the engagement and success of commencing students

There is widespread recognition that higher education institutions (HEIs) must actively support commencing students to ensure equity in access to the opportunities afforded by higher education. This role is particularly critical for students who because of educational, cultural or financial disadvantage or because they are members of social groups currently under-represented in higher education, may require additional transitional support to “level the playing field.” The challenge faced by HEIs is to provide this “support” in a way that is integrated into regular teaching and learning practices and reaches all commencing students. The Student Success Program (SSP) is an intervention in operation at the Queensland University of Technology (QUT) designed to identify and support those students deemed to be at risk of disengaging from their learning and their institution. Two sets of evidence of the impact of the SSP are presented: First, its expansion (a) from a one-faculty pilot project (Nelson, Duncan & Clarke, 2009) to all faculties and (b) into a variety of applications mirroring the student life cycle; and second, an evaluation of the impact of the SSP on students exposed to it. The outcomes suggest that: the SSP is an example of good practice that can be successfully applied to a variety of learning contexts and student enrolment situations; and the impact of the intervention on student persistence is sustained for at least 12 months and positively influences student retention. It is claimed that the good practice evidenced by the SSP is dependent on its integration into the broader First Year Experience Program at QUT as an example of transition pedagogy in action.