Design of Catalyst Interfaces for Heterogeneous Dihydrogen Production Manifolds and Incorporation into Photocathode Systems.

Engineering solar-powered catalyst systems for fuel production is of critical importance to the advancement of the global energy economy. Heterogeneous catalyst manifolds most promising for photocatalysis are those that boast versatile and cheap, stable components. Huisgen’s 1,3-dipolar cycloaddition (‘click’ chemistry) and π-stacking graphene adsorption systems provide a range of facile methods for electrode-surface modification and catalyst binding to build stable photocathode systems. Prior to this work, CoIII bis(benzenedithiolate) catalysts had been reported as active proton reduction catalysts in homogeneous phase. Due to the novelty of these complexes for use as proton reduction catalysts, no work prior to that reported in this thesis has attempted to heterogenize cobalt bis(dithiolene) catalysts and attach them to semiconductor surfaces. While several hydrogen production catalyst systems had been reported electrostatically adsorbed to graphitic supports, these studies lacked in-depth analysis of the ligand and graphitic support’s effects on catalyst adsorption, activity and retention on the surface. Previous studies have succeeded in functionalizing several semiconductor surfaces (such as silicon) with alkyne or azide groups; however, such modification of gallium-based 3,5-semiconductor systems containing an inherently strong driving force for proton reduction was previously unreported. Finally, previous literature examples of hydrogen production catalysts electrostatically adsorbed on graphene-coated semiconductors were relatively scarce, and were severely outweighed by work on covalent catalyst tethered systems. This work has for the first time heterogenized cobalt bis(dithiolene) complexes, a new class of H2 production catalysts, on graphitic supports and further attached the catalysts to the surface of GaP by means of the graphitic interface. These studies have provided insight into how the catalyst ligand structure and even the type of carbon in the interface can affect catalyst loading, activity and retention on the surface of the support. Initial studies of graphene- and Click-catalyst interfaces on gallium phosphide surfaces reported here represent some of the first examples of such interface development on these materials. These results push the edge of knowledge in solar-to-fuel conversion by expanding possibilities in the design of inexpensive, robust and easily modifiable photocathode systems with interchangeable catalyst and semiconductor components.PhDChemistryUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/120802/1/sceady_1.pd

Literacy practitioners’ perspectives on adult learning needs and technology approaches in Indigenous communities

Current reports of literacy rates in Australia indicate an ongoing gap in literacy skills between Indigenous and non-Indigenous Australian adults, at a time when the literacy demands of work and life are increasing. There are many perspectives on what are the literacy needs of Indigenous adults,from the perspectives of community members themselves to the relatively under-researched perspective of literacy practitioners. This paper provides the insights, experiences and recommendations from adult literacy practitioners who work with adult Indigenous learners in communities across Australia. Focus group interviews, using an online synchronous platform, were used to elicit views about the literacy needs of Indigenous adults in communities and the successes in and barriers to meeting those needs. The practitioners also shared their views on the use of technology in literacy learning. Together, these views can informfuture directions in curriculum design and teaching approaches for community-based Indigenous adult literacy education

Larval developmental temperature and ambient temperature affect copulation duration in a seed beetle

The effects of temperature on cellular, systemic and whole-organism processes can be short-term, acting within seconds or minutes of a temperature change, or long-term, acting across ontogenetic stages to affect an organism’s morphology, physiology and behavioural phenotype. Here we examine the effect of larval development temperature on adult copulatory behaviour in the bruchid beetle, Callosobruchus maculatus. As predicted by temperature’s kinetic effects, copulation duration was longest at the lowest ambient temperature. However, where ambient temperature was fixed and developmental temperature experimentally varied, males reared at the highest temperature were least likely to engage in copulation, whilst those reared at the lowest temperature copulated for longer. Previous research has shown males reared at cooler temperatures inseminate fewer sperm. Thus, in this species longer copulations are associated with reduced sperm transfer. We argue that knowledge of preceding ontogenetic conditions will help to elucidate the causes of variation in copulatory behaviour

Re-positioning SoTL toward the T-shaped Community

Amongst a range of changes that have taken place within tertiary education, perhaps the most revolutionary has been a shift to student-centred approaches focused on life-long learning. Accompanying this approach to holistic higher education (HE) has been a growing interest in, and understanding of, the Scholarship of Teaching and Learning (SoTL). SoTL has, at its core, a deep concern with student learning and is therefore well-aligned with higher education’s renewed focus on its students. In this conceptual paper, we examine the impact of the T-shaped person which many tertiary institutions are operationalizing to inform and connect the development of students’ deep disciplinary knowledge with non-academic and employment readiness skills (such as communication, problem-solving, teamwork, and critical thinking). Importantly, we argue for a re-positioning of SoTL to complement and support this model, with SoTL as both the fulcrum and the fluid, multiple threads of discourse that are intricately entwined around the structure of the T-shaped model. We encourage our colleagues to strive to be T-shaped practitioners and we cast a vision of a T-shaped community. Here, all stakeholders within HE connect both their academic knowledge and holistic skills in collaborative ways to produce learners who flourish in modern society. The SoTL community plays a pivotal role in achieving this vision and is well-positioned to expand the current notion of SoTL toward a more holistic, interconnected, central role in HE

On the feasibility of N2 fixation via a single-site FeI/FeIV cycle: Spectroscopic studies of FeI(N2)FeI, FeIV=N, and related species

The electronic properties of an unusually redox-rich iron system, [PhBPR 3]FeNx (where [PhBPR 3] is [PhB(CH2PR2)3]−), are explored by Mössbauer, EPR, magnetization, and density-functional methods to gain a detailed picture regarding their oxidation states and electronic structures. The complexes of primary interest in this article are the two terminal iron(IV) nitride species, [PhBPiPr 3]FeN (3a) and [PhBPCH2Cy 3]FeN (3b), and the formally diiron(I) bridged-Fe(μ-N2)Fe species, {[PhBPiPr 3]Fe}2(μ-N2) (4). Complex 4 is chemically related to 3a via a spontaneous nitride coupling reaction. The diamagnetic iron(IV) nitrides 3a and 3b exhibit unique electronic environments that are reflected in their unusual Mössbauer parameters, including quadrupole-splitting values of 6.01(1) mm/s and isomer shift values of −0.34(1) mm/s. The data for 4 suggest that this complex can be described by a weak ferromagnetic interaction (J/D < 1) between two iron(I) centers. For comparison, four other relevant complexes also are characterized: a diamagnetic iron(IV) trihydride [PhBPiPr 3]Fe(H)3(PMe3) (5), an S = 3/2 iron(I) phosphine adduct [PhBPiPr 3]FePMe3 (6), and the S = 2 iron(II) precursors to 3a, [PhBPiPr 3]FeCl and [PhBPiPr 3]Fe-2,3:5,6-dibenzo-7-aza bicyclo[2.2.1]hepta-2,5-diene (dbabh). The electronic properties of these respective complexes also have been explored by density-functional methods to help corroborate our spectral assignments and to probe their electronic structures further

Negative phenotypic and genetic associations between copulation duration and longevity in male seed beetles

Reproduction can be costly and is predicted to trade-off against other characters. However, while these trade-offs are well documented for females, there has been less focus on aspects of male reproduction. Furthermore, those studies that have looked at males typically only investigate phenotypic associations, with the underlying genetics often ignored. Here, we report on phenotypic and genetic trade-offs in male reproductive effort in the seed beetle, Callosobruchus maculatus. We find that the duration of a male's first copulation is negatively associated with subsequent male survival, phenotypically and genetically. Our results are consistent with life-history theory and suggest that like females, males trade-off reproductive effort against longevity

Enzyme-catalyzed mechanism of isoniazid activation in class I and class III peroxidases.

There is an urgent need to understand the mechanism of activation of the frontline anti-tuberculosis drug isoniazid by the Mycobacterium tuberculosis catalase-peroxidase. To address this, a combination of NMR spectroscopic, biochemical, and computational methods have been used to obtain a model of the frontline anti-tuberculosis drug isoniazid bound to the active site of the class III peroxidase, horseradish peroxidase C. This information has been used in combination with the new crystal structure of the M. tuberculosis catalase-peroxidase to predict the mode of INH binding across the class I heme peroxidase family. An enzyme-catalyzed mechanism for INH activation is proposed that brings together structural, functional, and spectroscopic data from a variety of sources. Collectively, the information not only provides a molecular basis for understanding INH activation by the M. tuberculosis catalase-peroxidase but also establishes a new conceptual framework for testing hypotheses regarding the enzyme-catalyzed turnover of this compound in a number of heme peroxidases

The counter-propagating Rossby-wave perspective on baroclinic instability. II: Application to the Charney model

The constant-density Charney model describes the simplest unstable basic state with a planetary-vorticity gradient, which is uniform and positive, and baroclinicity that is manifest as a negative contribution to the potential-vorticity (PV) gradient at the ground and positive vertical wind shear. Together, these ingredients satisfy the necessary conditions for baroclinic instability. In Part I it was shown how baroclinic growth on a general zonal basic state can be viewed as the interaction of pairs of ‘counter-propagating Rossby waves’ (CRWs) that can be constructed from a growing normal mode and its decaying complex conjugate. In this paper the normal-mode solutions for the Charney model are studied from the CRW perspective. Clear parallels can be drawn between the most unstable modes of the Charney model and the Eady model, in which the CRWs can be derived independently of the normal modes. However, the dispersion curves for the two models are very different; the Eady model has a short-wave cut-off, while the Charney model is unstable at short wavelengths. Beyond its maximum growth rate the Charney model has a neutral point at finite wavelength (r=1). Thereafter follows a succession of unstable branches, each with weaker growth than the last, separated by neutral points at integer r—the so-called ‘Green branches’. A separate branch of westward-propagating neutral modes also originates from each neutral point. By approximating the lower CRW as a Rossby edge wave and the upper CRW structure as a single PV peak with a spread proportional to the Rossby scale height, the main features of the ‘Charney branch’ (0<r<1) can be deduced without prior calculation of the normal modes. Furthermore, CRWs from this branch are seen to make a smooth transition into the boundary and interior PV structure of the neutral modes appearing at r=1. The behaviour of the other branches and neutral points is essentially the same when viewed from the CRW perspective, but with cancelling interior PV structures reducing the self and mutual interaction of the CRWs. The underlying dynamics determining the nature of all the solutions is the difference in the scale-dependence of PV inversion for boundary and interior PV anomalies, the Rossby-wave propagation mechanism and the CRW interaction. The behaviour of the Charney modes and the first neutral branch, which rely on tropospheric PV gradients, are arguably more applicable to the atmosphere than modes of the Eady model where the positive PV gradient exists only at the tropopaus