Structural studies on silver(I) complexes containing phenylcyanamido ligands and uranyl(VI) complexes with beta-ketophenolates : a dissertation presented in partial fulfilment for the degree of Master of Science in Chemistry at Massey University

This thesis is divided into two parts. In Section One studies on the interaction of phenylcyanamides with silver(I) are reported. Section Two describes the results of studies on the complexes formed from β-ketophenol ligands and the uranyl ion. Section One Chapter 1 is a brief overview of the use of phenylcyanamides in forming coordination complexes with transition metals. In Chapter 2 the preparation of a series of silver complexes of the general formula [Ag(Ph₃P)₃(pcyd)], where pcyd is a phenylcyanamido anion, is described. The crystal structures of [Ag(Ph₃P)₃(4-Brpcyd)] and [Ag(Ph₃P)₃(4-MeOpcyd)] have been determined, in which the silver atom occupies a distorted tetrahedral environment, and the latter complex has a very short terminal C-N bond within the 4-methoxyphenylcyanamido ligand. Chapter 3 provides a comparison of all those transition metal complexes of phenylcyanamides that have been structurally characterised. Section Two Chapter 4 is a brief overview of the use of β-diketonate ligands in forming dinuclear complexes, especially those in which the uranyl ion (UO₂²+) is present. In Chapter 5 the preparation of the mononuclear complexes [UO₂(HL¹)₂(MeOH)], (UO₂(HL²)₂(EtOH)], the heterobinuclear complexes [U0₂Mn(L¹)₂(EtOH)]·1.5H₂O, and [UO₂Mn(L²)₂(EtOH)]·2H₂₂O and the oxo-ligand adducts [UO₂(HL¹)₂(Ph₃AsO)]·2H₂O, [U0₂(HL²)₂(Ph₃PO)] and [UO₂(HL²)₂(Ph₃AsO)] (H₂L¹ = 1-(2-hydroxyphenyl)-3- butanedione and H₂L² = 1-(2-hydroxyphenyl)-3-phenyl-l,3-propanedione) is described. The complexes have been characterized by a variety of physicochemical techniques and the crystal structures of [UO₂(HL¹)₂(EtOH)] and [UO₂(HL²)₂(EtOH)]·EtOH determined. Both complexes contain seven coordinate uranium(VI) in a pentagonal bipyramidal geometry in which the two bidentate β-diketonato ligands and the ethanol ligand make up the equatorial pentagonal plane. For the complex [UO₂(HL¹)₂(EtOH)] the HL¹ ligands are in a trans arrangement with respect to one another, whereas for the [UO₂(HL²)₂(EtOH)]·EtOH complex the HL² ligands adopt a cis arrangement. However, in solution variable temperature ¹H NMR spectra indicate that the cis and trans isomers are in equilibrium for both complexes

Vector lattices with a Hausdorff uo-Lebesgue topology

We investigate the construction of a Hausdorff uo-Lebesgue topology on a vector lattice from a Hausdorff (o)-Lebesgue topology on an order dense ideal, and what the properties of the topologies thus obtained are. When the vector lattice has an order dense ideal with a separating order continuous dual, it is always possible to supply it with such a topology in this fashion, and the restriction of this topology to a regular sublattice is then also a Hausdorff uo-Lebesgue topology. A regular vector sublattice of $\mathrm{L}_0(X,\Sigma,\mu)$ for a semi-finite measure $\mu$ falls into this category, and the convergence of nets in its Hausdorff uo-Lebesgue topology is then the convergence in measure on subsets of finite measure. When a vector lattice not only has an order dense ideal with a separating order continuous dual, but also has the countable sup property, we show that every net in a regular vector sublattice that converges in its Hausdorff uo-Lebesgue topology always contains a sequence that is uo-convergent to the same limit. This enables us to give satisfactory answers to various topological questions about uo-convergence in this context.Comment: 37 pages. Minor changes; a few references added. Final version, to appear in J. Math. Anal. App

Unbounded order convergence in dual spaces

A net $(x_\alpha)$ in a vector lattice $X$ is said to be {unbounded order convergent} (or uo-convergent, for short) to $x\in X$ if the net (\abs{x_\alpha-x}\wedge y) converges to 0 in order for all $y\in X_+$. In this paper, we study unbounded order convergence in dual spaces of Banach lattices. Let $X$ be a Banach lattice. We prove that every norm bounded uo-convergent net in $X^*$ is $w^*$-convergent iff $X$ has order continuous norm, and that every $w^*$-convergent net in $X^*$ is uo-convergent iff $X$ is atomic with order continuous norm. We also characterize among $\sigma$-order complete Banach lattices the spaces in whose dual space every simultaneously uo- and $w^*$-convergent sequence converges weakly/in norm

A universal ontology-based approach to data integration

One of the main problems in building data integration systems is that of semantic integration. It has been acknowledged that the problem would not exist if all systems were developed using the same global schema, but so far, such global schema has been considered unfeasible in practice. However, in our previous work, we have argued that given the current state-of-the-art, a global schema may be feasible now, and we have put forward a vision of a Universal Ontology (UO) that may be desirable, feasible, and viable. One of the reasons why the UO may be desirable is that it might solve the semantic integration problem. The objective of this paper is to show that indeed the UO could solve, or at least greatly alleviate, the semantic integration problem. We do so by presenting an approach to semantic integration based on the UO that requires much less effort than other approaches.Peer ReviewedPostprint (published version

Application of Semi-Empirical Ventilation Models in A Mediterranean Greenhouse with Opposing Thermal and Wind Effects. Use of Non-Constant Cd (Pressure Drop Coefficient Through the Vents) and Cw (Wind Effect Coefficient)

The present work analyses the natural ventilation of a multi-span greenhouse with one roof vent and two side vents by means of sonic anemometry. Opening the roof vent to windward, one side vent to leeward, and the other side vents to windward (this last vent obstructed by another greenhouse), causes opposing thermal GT (m3 s−1) and wind effects Gw (m3 s−1), as outside air entering the greenhouse through the roof vent circulates downward, contrary to natural convection due to the thermal effect. In our case, the ventilation rate RM (h−1) in a naturally ventilated greenhouse fits a second order polynomial with wind velocity uo (RM = 0.37 uo2 + 0.03 uo + 0.75; R2 = 0.99). The opposing wind and thermal effects mean that ventilation models based on Bernoulli’s equation must be modified in order to add or subtract their effects accordingly—Model 1, in which the flow is driven by the sum of two independent pressure fields GM1=√(∣∣G2T±G2w∣∣) , or Model 2, in which the flow is driven by the sum of two independent fluxes GM2=|GT±Gw| . A linear relationship has been obtained, which allows us to estimate the discharge coefficient of the side vents (CdVS) and roof vent (CdWR) as a function of uo [CdVS = 0.028 uo + 0.028 (R2 = 0.92); CdWR = 0.036 uo + 0.040 (R2 = 0.96)]. The wind effect coefficient Cw was determined by applying models M1 and M2 proved not to remain constant for the different experiments, but varied according to the ratio uo/∆Tio0.5 or δ [CwM1 = exp(−2.693 + 1.160/δ) (R2 = 0.94); CwM2 = exp(−2.128 + 1.264/δ) (R2 = 0.98)]

Optimal Time Consistent Monetary Policy

We discuss the issue of time consistency of monetary policy. We develop a simple and intuitive procedure to derive analytically the unconditionally optimal (UO) policy in a general linear-quadratic set-up, a perspective stressed by Taylor (1979) and Whiteman (1986). We compare the UO perspective on optimal monetary policy with alternative approaches. We use our approach in simple backward- and forward-looking models and argue that the UO perspective is worthy of renewed interest.Time consistency, unconditional expectation, timeless perspective, optimal policy.

Daylight adaptive optimal lighting system control strategies for energy savings and visual comfort in commercial buildings

Artificial lighting of commercial buildings in Malaysia consumes 21% of the total electrical energy. Therefore, reducing the energy is required to achieve sustainable buildings (i.e., higher energy efficiency and visual comfort), by implementing optimal light sensor placement method and optimisation-based control strategy. However, in recent works related to light sensor placement, energy performance and illuminance uniformity (Uo) are not considered, and the results did not provide the optimal number of sensors to be employed. To optimise power consumption (PC) and visual comfort simultaneously through the optimisation-based control strategy, the previous work developed a visual comfort model to represent Uo. However, the model did not consider daylight and the results of Uo need further improvement. This research proposes: (1) a new optimal light sensor placement method (OLSPM) by using combined particle swarm optimisation (PSO) and fuzzy logic controller (FLC) denoted as OLSPM-PSOFLC, and (2) a new visual comfort metric called illuminance uniformity deviation index (IUDI) and incorporated with multi-objective PSO (MOPSO) for solving energy consumption and visual comfort problem. The OLSPM�PSOFLC is developed to determine the optimal number and position of light sensors by considering PC while satisfying average illuminance level (Eav) and Uo. To ensure both PC and Uo in the room are always at the optimum levels, the IUDI with MOPSO is developed. Before the proposed methods are implemented, retrofitting lighting system is implemented first to determine the best lamp technology to be installed in terms of technical and economic metrics. An actual office room is considered for carrying out the proposed methods. The comparative results showed that the OLSPM�PSOFLC significantly reduced the number of sensors, energy consumption, carbon dioxide emission, payback period, and life cycle cost were 66%, 23%, 23%, and 30%, respectively, compared to the multi-sensor. Meanwhile, based on the comparative study of the IUDI and CVRMSE, the IUDI showed superior performance with 6% and 27% improvement of Uo and energy savings, respectively. Based on their superiority, the newly developed methods can be potentially implemented for all types of rooms and are very useful methodologies towards sustainable commercial buildings