Characterisation and Estimation of Entropy Rate for Long Range Dependent Processes

Much of the theory of random processes has been developed with the assumption that distant time periods are weakly correlated. However, it has been discovered in many real-world phenomena that this assumption is not valid. These findings have resulted in extensive research interest into stochastic processes that have strong correlations that persist over long time periods. This phenomenon is called long range dependence. This phenomena has been defined in the time and frequency domains by the slow decay of their autocorrelation function and the existence of a pole at the origin of the spectral density function, respectively. Information theory has proved very useful in statistics and probability theory. However, there has not been much research into the information theoretic properties and characterisations of this phenomena.This thesis characterises the phenomena of long range dependence, for discrete and continuous-valued stochastic processes in discrete time, by an information theoretic measure, the entropy rate. The entropy rate measures the amount of information contained in a stochastic process on average, per random variable. Common characterisations of long range dependence in the time and frequency domains are given by the slow convergence to quantities of interest, such as the sample mean. We show that this type of behaviour is present in the entropy rate function, by showing that long range dependence also has slow convergence of the conditional entropy to the entropy rate, due to some entropic quantities diverging to infinity. As an extension we show for classes of Gaussian processes and Markov chains that long range dependence by an infinite amount of shared information between the past and future of a stochastic process. The slow convergence has the impact of making accurate estimation of the differential entropy rate on data from long range dependent processes difficult, to the extent that existing techniques either are not accurate or are computationally intensive. We introduce a new estimation technique, that is able to balance these two concerns and make quick and accurate estimates of the differential entropy rate from continuous-valued data. We develop and utilise a connection between the differential entropy rate and the Shannon entropy rate of its quantised process as the basis of the estimation technique. This allows us to draw on the extensive research into Shannon entropy rate estimation on discrete-valued data, and we show that properties for the differential entropy rate estimator can be inherited from the choice of Shannon entropy rate estimator.Thesis (Ph.D.) -- University of Adelaide, School of Mathematical Sciences, 202

Catalyst-Controlled Stereoselective Olefin Metathesis as a Principal Strategy in Multistep Synthesis Design: A Concise Route to (+)-Neopeltolide

Molybdenum-, tungsten-, and ruthenium-based complexes that control the stereochemical outcome of olefin metathesis reactions have been recently introduced. However, the complementary nature of these systems through their combined use in multistep complex molecule synthesis has not been illustrated. A concise diastereo- and enantioselective route that furnishes the anti-proliferative natural product neopeltolide is now disclosed. Catalytic transformations are employed to address every stereochemical issue. Among the featured processes are an enantioselective ring-opening/cross-metathesis promoted by a Mo monoaryloxide pyrrolide (MAP) complex and a macrocyclic ring-closing metathesis that affords a trisubstituted alkene and is catalyzed by a Mo bis(aryloxide) species. Furthermore, Z-selective cross-metathesis reactions, facilitated by Mo and Ru complexes, have been employed in the stereoselective synthesis of the acyclic dienyl moiety of the target molecule.National Institutes of Health (U.S.) (NIH grant GM-59426)National Institutes of Health (U.S.) (NIH grant GM-57212)AstraZeneca (Firm) (Graduate Fellowship)National Science Foundation (U.S.) (NSF award CHE-1362763

Nonhalogenated organic molecules from Laurencia algae

The marine red algae of the genus Laurencia have produced more 700 secondary metabolites and exhibited high molecular diversity and intriguing bioactivity. Since the halogenated structures have been comprehensively reviewed previously, this review, covering up to the end of 2012, mainly focuses on the source, structure elucidation, and bioactivity of nonhalogenated organic molecules from Laurencia spp. as well as the relationship between nonhalogenated and halogenated products. Overall, 173 new or new naturally occurring compounds with 58 skeletons, mainly including sesquiterpenes, diterpenes, triterpenes, and C15-acetogenins, are described.The marine red algae of the genus Laurencia have produced more 700 secondary metabolites and exhibited high molecular diversity and intriguing bioactivity. Since the halogenated structures have been comprehensively reviewed previously, this review, covering up to the end of 2012, mainly focuses on the source, structure elucidation, and bioactivity of nonhalogenated organic molecules from Laurencia spp. as well as the relationship between nonhalogenated and halogenated products. Overall, 173 new or new naturally occurring compounds with 58 skeletons, mainly including sesquiterpenes, diterpenes, triterpenes, and C-15-acetogenins, are described