Stochastic chemical kinetics and the quasi-steady-state assumption : application to the stochastic simulation algorithm and chemical master equation

Recently the application of the quasi-steady-state approximation (QSSA) to the stochastic simulation algorithm (SSA) was suggested for the purpose of speeding up stochastic simulations of chemical systems that involve both relatively fast and slow chemical reactions [Rao and Arkin, J. Chem. Phys. 118, 4999 (2003)] and further work has led to the nested and slow-scale SSA. Improved numerical efficiency is obtained by respecting the vastly different time scales characterizing the system and then by advancing only the slow reactions exactly, based on a suitable approximation to the fast reactions. We considerably extend these works by applying the QSSA to numerical methods for the direct solution of the chemical master equation (CME) and, in particular, to the finite state projection algorithm [Munsky and Khammash, J. Chem. Phys. 124, 044104 (2006)], in conjunction with Krylov methods. In addition, we point out some important connections to the literature on the (deterministic) total QSSA (tQSSA) and place the stochastic analogue of the QSSA within the more general framework of aggregation of Markov processes. We demonstrate the new methods on four examples: Michaelis–Menten enzyme kinetics, double phosphorylation, the Goldbeter–Koshland switch, and the mitogen activated protein kinase cascade. Overall, we report dramatic improvements by applying the tQSSA to the CME solver.

Lignocellulosics as a renewable feedstock for chemical industry : chemical hydrolysis and pretreatment processes

Lignocellulosic materials including agricultural, municipal and forestry residues, and dedicated bioenergy crops offer significant potential as a renewable feedstock for the production of fuels and chemicals. These products can be chemically or functionally equivalent to existing products that are produced from fossil-based feedstocks. To unlock the potential of lignocellulosic materials, it is necessary to pretreat or fractionate the biomass to make it amenable to downstream processing. This chapter explores current and developing technologies for the pretreatment and fractionation of lignocellulosic biomass for the production of chemicals and fuels.

Stochastic simulation of chemical reactions in spatially complex media

Discrete stochastic simulations, via techniques such as the Stochastic Simulation Algorithm (SSA) are a powerful tool for understanding the dynamics of chemical kinetics when there are low numbers of certain molecular species. However, an important constraint is the assumption of well-mixedness and homogeneity. In this paper, we show how to use Monte Carlo simulations to estimate an anomalous diffusion parameter that encapsulates the crowdedness of the spatial environment. We then use this parameter to replace the rate constants of bimolecular reactions by a time-dependent power law to produce an SSA valid in cases where anomalous diffusion occurs or the system is not well-mixed (ASSA). Simulations then show that ASSA can successfully predict the temporal dynamics of chemical kinetics in a spatially constrained environment.

Nanoherding : plasma-chemical synthesis and electric-charge-driven self organization of SiO2 nanodots

We report on the chemical synthesis of the arrays of silicon oxide nanodots and their self-organization on the surface via physical processes triggered by surface charges. The method based on chemically active oxygen plasma leads to the rearrangement of nanostructures and eventually to the formation of groups of nanodots. This behavior is explained in terms of the effect of electric field on the kinetics of surface processes. The direct measurements of the electric charges on the surface demonstrate that the charge correlates with the density and arrangement of nanodots within the array. Extensive numerical simulations support the proposed mechanism and prove a critical role of the electric charges in the self-organization. This simple and environment-friendly self-guided process could be used in the chemical synthesis of large arrays of nanodots on semiconducting surfaces for a variety of applications in catalysis, energy conversion and storage, photochemistry, environmental and biosensing, and several others.

Framework and processes for enhancing sustainability deliverables in Australian road infrastructure projects

Road and highway infrastructure provides the backbone for a nation’s economic growth. The versatile dispersion of population in Australia and its resource boom, coupled with improved living standards and growing societal expectations, calls for continuing development and improvement of road infrastructure under the current local, state and federal governments’ policies and strategic plans. As road infrastructure projects involve huge resources and mechanisms, achieving sustainability not only on economic scales but also through environmental and social responsibility becomes a crucial issue. While sustainability is a logical link to infrastructure development, literature study and consultation with the industry found that there is a lack of common understanding on what constitutes sustainability in the infrastructure context. Its priorities are often interpreted differently among multiple stakeholders. For road infrastructure projects which typically span over long periods of time, achieving tangible sustainability outcomes during the lifecycle of development remains a formidable task. Sustainable development initiatives often remain ideological as in macro-level policies and broad-based concepts. There were little elaboration and exemplar cases on how these policies and concepts can be translated into practical decision-making during project implementation. In contrast, there seemed to be over commitment on research and development of sustainability assessment methods and tools. Between the two positions, there is a perception-reality gap and mismatch, specifically on how to enhance sustainability deliverables during infrastructure project delivery. Review on past research in this industry sector also found that little has been done to promote sustainable road infrastructure development; this has wide and varied potential impacts. This research identified the common perceptions and expectations by different stakeholders towards achieving sustainability in road and highway infrastructure projects. Face to face interviews on selected representatives of these stakeholders were carried out in order to select and categorize, confirm and prioritize a list of sustainability performance targets identified through literature and past research. A Delphi study was conducted with the assistance of a panel of senior industry professionals and academic experts, which further considered the interrelationship and influence of the sustainability indicators, and identified critical sustainability indicators under ten critical sustainability criteria (e.g. Environmental, Health & Safety, Resource Utilization & Management, Social & Cultural, Economic, Public Governance & Community Engagement, Relations Management, Engineering, Institutional and Project Management). This presented critical sustainability issues that needed to be addressed at the project level. Accordingly, exemplar highway development projects were used as case studies to elicit solutions for the critical issues. Through the identification and integration of different perceptions and priority needs of the stakeholders, as well as key sustainability indicators and solutions for critical issues, a set of decision-making guidelines was developed to promote and drive consistent sustainability deliverables in road infrastructure projects.

Queer/error : gay media systems and processes of abjection

Gay community media functions as a system with three nodes, in which the flows of information and capital theoretically benefit all parties: the gay community gains a sense of cohesion and citizenship through media; the gay media outlets profit from advertisers’ capital; and advertisers recoup their investments in lucrative ‘pink dollar’ revenue. But if a necessary corollary of all communication systems is error or noise, where—and what—are the errors in this system? In this paper we argue that the ‘error’ in the gay media system is Queerness, and that the gay media system ejects (in a process of Kristevan abjection) these Queer identities in order to function successfully. We examine the ways in which Queer identities are excluded from representation in such media through a discourse and content analysis of The Sydney Star Observer (Australia’s largest gay and lesbian paper). First, we analyse the way Queer bodies are excluded from the discourses that construct and reinforce both the ideal gay male body and the notions of homosexual essence required for that body to be meaningful. We then argue that abject Queerness returns in the SSO’s discourses of public health through the conspicuous absence of the AIDS-inflicted body (which we read as the epitome of the abject Queer), since this absence paradoxically conjures up a trace of that which the system tries to expel. We conclude by arguing that because the ‘Queer error’ is integral to the SSO, gay community media should practise a politics of Queer inclusion rather than exclusion.

Nitrone [2]rotaxanes: Simultaneous chemical protection and electrochemical activation of a functional group

We report on the use of the hydrogen bond accepting properties of neutral nitrone moieties to prepare benzylic-amide-macrocycle-containing [2]rotaxanes in yields as high as 70 %. X-Ray crystallography shows the presence of up to four intercomponent hydrogen bonds between the amide groups of the macrocycle and the two nitrone groups of the thread. Dynamic 1H NMR studies of the rates of macrocycle pirouetting in nonpolar solutions indicate that amide-nitrone hydrogen bonds are particularly strong, ~1.3 and ~0.2 kcal mol-1 stronger than similar amide-ester and amide-amide interactions, respectively. In addition to polarizing the N-O bond through hydrogen bonding, the rotaxane structure affects the chemistry of the nitrone groups in two significant ways: The intercomponent hydrogen bonding activates the nitrone groups to electrochemical reduction, a one electron reduction of the rotaxane being stablized by a remarkable 400 mV (8.1 kcal mol-1) with respect to the same process in the thread; encapsulation, however, protects the same functional groups from chemical reduction with an external reagent (and slows down electron transfer to and from the electroactive groups in cyclicvoltammetry experiments). Mechanical interlocking with a hydrogen bonding molecular sheath thus provides a route to an encapsulated polarized functional group and radical anions of significant kinetic and thermodynamic stability.

Boundary weaving : the social structure and processes of organizational boundaries

Boundaries are an important field of study because they mediate almost every aspect of organizational life. They are becoming increasingly more important as organizations change more frequently and yet, despite the endemic use of the boundary metaphor in common organizational parlance, they are poorly understood. Organizational boundaries are under-theorized and researchers in related fields often simply assume their existence, without defining them. The literature on organizational boundaries is fragmented with no unifying theoretical basis. As a result, when it is recognized that an organizational boundary is "dysfunctional". there is little recourse to models on which to base remediating action. This research sets out to develop just such a theoretical model and is guided by the general question: "What is the nature of organizational boundaries?" It is argued that organizational boundaries can be conceptualised through elements of both social structure and of social process. Elements of structure include objects, coupling, properties and identity. Social processes include objectification, identification, interaction and emergence. All of these elements are integrated by a core category, or basic social process, called boundary weaving. An organizational boundary is a complex system of objects and emergent properties that are woven together by people as they interact together, objectifying the world around them, identifying with these objects and creating couplings of varying strength and polarity as well as their own fragmented identity. Organizational boundaries are characterised by the multiplicity of interconnections, a particular domain of objects, varying levels of embodiment and patterns of interaction. The theory developed in this research emerged from an exploratory, qualitative research design employing grounded theory methodology. The field data was collected from the training headquarters of the New Zealand Army using semi-structured interviews and follow up observations. The unit of analysis is an organizational boundary. Only one research context was used because of the richness and multiplicity of organizational boundaries that were present. The model arose, grounded in the data collected, through a process of theoretical memoing and constant comparative analysis. Academic literature was used as a source of data to aid theory development and the saturation of some central categories. The final theory is classified as middle range, being substantive rather than formal, and is generalizable across medium to large organizations in low-context societies. The main limitation of the research arose from the breadth of the research with multiple lines of inquiry spanning several academic disciplines, with some relevant areas such as the role of identity and complexity being addressed at a necessarily high level. The organizational boundary theory developed by this research replaces the typology approaches, typical of previous theory on organizational boundaries and reconceptualises the nature of groups in organizations as well as the role of "boundary spanners". It also has implications for any theory that relies on the concept of boundaries, such as general systems theory. The main contribution of this research is the development of a holistic model of organizational boundaries including an explanation of the multiplicity of boundaries . no organization has a single definable boundary. A significant aspect of this contribution is the integration of aspects of complexity theory and identity theory to explain the emergence of higher-order properties of organizational boundaries and of organizational identity. The core category of "boundary weaving". is a powerful new metaphor that significantly reconceptualises the way organizational boundaries may be understood in organizations. It invokes secondary metaphors such as the weaving of an organization's "boundary fabric". and provides managers with other metaphorical perspectives, such as the management of boundary friction, boundary tension, boundary permeability and boundary stability. Opportunities for future research reside in formalising and testing the theory as well as developing analytical tools that would enable managers in organizations to apply the theory in practice.