Modeling of sonochemical decomposition of CCI4 in aqueous solutions

In the context of removal of organic pollutants from wastewater, sonolysis of CCl4 dissolved in water has been widely investigated. These investigations are either completely experimental or correlate data empirically. In this work, a quantitative model is developed to predict the rate of sonolysis of aqueous CCl4. The model considers the isothermal growth and partially adiabatic collapse of cavitation bubbles containing gas and vapor leading to conditions of high temperatures and pressures in them, attainment of thermodynamic equilibrium at the end of collapse, release of bubble contents into the liquid pool, and reactions in the well-mixed pool. The model successfully predicts the extent of degradation of dissolved CCl4, and the influence of various parameters such as initial concentration of CCl4, temperature, and nature of gas atmosphere above the liquid. in particular, it predicts the results of Hua and Hoffmann (Environ. Sci Technol, 1996, 30, 864-871), who found that degradation is first order with CCl4 and that Argon as well as Ar-O-3 atmospheres give the same results. The framework of the model is capable of quantitatively describing the degradation of many dissolved organics by considering all the involved species.

Nanoporous Pt with High Surface Area by Reaction-Limited Aggregation of Nanoparticles

Nanoporous structures with high active surface areas are critical for a variety of applications. Here, we present a general templateless strategy to produce such porous structures by controlled aggregation of nanostructured subunits and apply the principles for synthesizing nanoporous Pt for electrocatalytic oxidation of methanol. The nature of the aggregate produced is controlled by tuning the electrostatic interaction between surfactant-free nanoparticles in the solution phase. When the repulsive force between the particles is very large, the particles are stabilized in the solution while instantaneous aggregation leading to fractal-like structures results when the repulsive force is very low. Controlling the repulsive interaction to an optimum, intermediate value results in the formation of compact structures with very large surface areas. In the case of Pt, nanoporous clusters with an extremely high specific surface area (39 m(2)/g) and high activity for methanol oxidation have been produced. Preliminary investigations indicate that the method is general and can be easily extended to produce nanoporous structures of many inorganic materials.

Design-driven digital futures: The role of design-led innovation in the creation of online connected communities for new mobility solutions

Online communities have fundamentally changed how humans connected and are now so common they are fundamental to the human experience. As the Internet developed for Web 1.0 to Web 2.0, the functionality of these communities has far exceeded initial expectations. These communities have shifted from simply places to share information to ways to access products and services that bridge the online and offline worlds. This shift has led to the disruption of many industries with the transportation industry being one such sector. Both private transport providers and public transport systems face competition from online communities who are able to link services providers and customers more effectively and innovatively. These types of communities fall under what has been popularised as collaborative consumption or the sharing economy. The aim of this study is to explore the role of Design-led Innovation in the creation of digital futures, specifically online connected communities for successful new mobility solutions. To explore this proposition multiple data collection methods are proposed;Content Analysis, ii) A Comparative Qualitative Study consisting of Qualitative Interviews and Focus Groups / Design Workshops and iii) An Action Research Cycle of Embedded Practice. The multidisciplinary nature of this study grounds this research in a novel position contributing to new knowledge in both the field of design, and also a deeper understanding of the larger fast-growing online community phenomena.

Factors influencing sustainability of health service innovation: Emergency nurse practitioner services

Introduction: Emergency department nurse practitioner services are one of the most frequently implemented service delivery models in Australian hospitals. This research examined factors influencing sustainability of this innovative service delivery model and offers some recommendations for future service integration. Background Many health service innovations have been implemented in an attempt to meet the growing demand for efficient, cost effective health care however, sustainability of many of these innovations has not been evaluated and is poorly understood. Aim The aim of the research was to identify factors that influence sustainability of emergency department nurse practitioner services and to operationalise a theoretical framework for evaluating innovation sustainability. Methodology The research used case study methodology. The case was emergency nurse practitioner services, and units of analysis were emergency department staff, emergency nurse practitioners and documents relating to nurse practitioner services. The data collection methods included, survey, one-on-one interviews, document analysis and telephone survey. Results This research shows that emergency nurse practitioner services partially comply with the factors of sustainability as described in the Sustainability of Innovation theoretical framework: Political, Organisational, Workforce, Financial and Innovation specific factors. Where services do not entirely meet the factors the existing benefits of the service may outweigh the barriers and other means of working around shortfalls are also implemented by staff to ensure patient safety. Conclusion The rapidly expanding emergency nurse practitioner service has been examined using case study methodology to find that certain factors may be threatening the sustainability of this health service innovation. Potentially an innovation may be sustained when only some factors are met in the short term, however, long term sustainability may be challenged if factors are not addressed and supported.

A linear programming approach for estimating the structure of a sparse linear genetic network from transcript profiling data

Background: A genetic network can be represented as a directed graph in which a node corresponds to a gene and a directed edge specifies the direction of influence of one gene on another. The reconstruction of such networks from transcript profiling data remains an important yet challenging endeavor. A transcript profile specifies the abundances of many genes in a biological sample of interest. Prevailing strategies for learning the structure of a genetic network from high-dimensional transcript profiling data assume sparsity and linearity. Many methods consider relatively small directed graphs, inferring graphs with up to a few hundred nodes. This work examines large undirected graphs representations of genetic networks, graphs with many thousands of nodes where an undirected edge between two nodes does not indicate the direction of influence, and the problem of estimating the structure of such a sparse linear genetic network (SLGN) from transcript profiling data. Results: The structure learning task is cast as a sparse linear regression problem which is then posed as a LASSO (l1-constrained fitting) problem and solved finally by formulating a Linear Program (LP). A bound on the Generalization Error of this approach is given in terms of the Leave-One-Out Error. The accuracy and utility of LP-SLGNs is assessed quantitatively and qualitatively using simulated and real data. The Dialogue for Reverse Engineering Assessments and Methods (DREAM) initiative provides gold standard data sets and evaluation metrics that enable and facilitate the comparison of algorithms for deducing the structure of networks. The structures of LP-SLGNs estimated from the INSILICO1, INSILICO2 and INSILICO3 simulated DREAM2 data sets are comparable to those proposed by the first and/or second ranked teams in the DREAM2 competition. The structures of LP-SLGNs estimated from two published Saccharomyces cerevisae cell cycle transcript profiling data sets capture known regulatory associations. In each S. cerevisiae LP-SLGN, the number of nodes with a particular degree follows an approximate power law suggesting that its degree distributions is similar to that observed in real-world networks. Inspection of these LP-SLGNs suggests biological hypotheses amenable to experimental verification. Conclusion: A statistically robust and computationally efficient LP-based method for estimating the topology of a large sparse undirected graph from high-dimensional data yields representations of genetic networks that are biologically plausible and useful abstractions of the structures of real genetic networks. Analysis of the statistical and topological properties of learned LP-SLGNs may have practical value; for example, genes with high random walk betweenness, a measure of the centrality of a node in a graph, are good candidates for intervention studies and hence integrated computational – experimental investigations designed to infer more realistic and sophisticated probabilistic directed graphical model representations of genetic networks. The LP-based solutions of the sparse linear regression problem described here may provide a method for learning the structure of transcription factor networks from transcript profiling and transcription factor binding motif data.

A new method for the in vivo identification of mechanical properties in arteries from cine MRI images: Theoretical framework and validation

Quantifying the stiffness properties of soft tissues is essential for the diagnosis of many cardiovascular diseases such as atherosclerosis. In these pathologies it is widely agreed that the arterial wall stiffness is an indicator of vulnerability. The present paper focuses on the carotid artery and proposes a new inversion methodology for deriving the stiffness properties of the wall from cine-MRI (magnetic resonance imaging) data. We address this problem by setting-up a cost function defined as the distance between the modeled pixel signals and the measured ones. Minimizing this cost function yields the unknown stiffness properties of both the arterial wall and the surrounding tissues. The sensitivity of the identified properties to various sources of uncertainty is studied. Validation of the method is performed on a rubber phantom. The elastic modulus identified using the developed methodology lies within a mean error of 9.6%. It is then applied to two young healthy subjects as a proof of practical feasibility, with identified values of 625 kPa and 587 kPa for one of the carotid of each subject.

Liquid Chromatography-Mass Spectrometry in Studies of Drug Metabolism and Permeability

Poor pharmacokinetics is one of the reasons for the withdrawal of drug candidates from clinical trials. There is an urgent need for investigating in vitro ADME (absorption, distribution, metabolism and excretion) properties and recognising unsuitable drug candidates as early as possible in the drug development process. Current throughput of in vitro ADME profiling is insufficient because effective new synthesis techniques, such as drug design in silico and combinatorial synthesis, have vastly increased the number of drug candidates. Assay technologies for larger sets of compounds than are currently feasible are critically needed. The first part of this work focused on the evaluation of cocktail strategy in studies of drug permeability and metabolic stability. N-in-one liquid chromatography-tandem mass spectrometry (LC/MS/MS) methods were developed and validated for the multiple component analysis of samples in cocktail experiments. Together, cocktail dosing and LC/MS/MS were found to form an effective tool for increasing throughput. First, cocktail dosing, i.e. the use of a mixture of many test compounds, was applied in permeability experiments with Caco-2 cell culture, which is a widely used in vitro model for small intestinal absorption. A cocktail of 7-10 reference compounds was successfully evaluated for standardization and routine testing of the performance of Caco-2 cell cultures. Secondly, cocktail strategy was used in metabolic stability studies of drugs with UGT isoenzymes, which are one of the most important phase II drug metabolizing enzymes. The study confirmed that the determination of intrinsic clearance (Clint) as a cocktail of seven substrates is possible. The LC/MS/MS methods that were developed were fast and reliable for the quantitative analysis of a heterogenous set of drugs from Caco-2 permeability experiments and the set of glucuronides from in vitro stability experiments. The performance of a new ionization technique, atmospheric pressure photoionization (APPI), was evaluated through comparison with electrospray ionization (ESI), where both techniques were used for the analysis of Caco-2 samples. Like ESI, also APPI proved to be a reliable technique for the analysis of Caco-2 samples and even more flexible than ESI because of the wider dynamic linear range. The second part of the experimental study focused on metabolite profiling. Different mass spectrometric instruments and commercially available software tools were investigated for profiling metabolites in urine and hepatocyte samples. All the instruments tested (triple quadrupole, quadrupole time-of-flight, ion trap) exhibited some good and some bad features in searching for and identifying of expected and non-expected metabolites. Although, current profiling software is helpful, it is still insufficient. Thus a time-consuming largely manual approach is still required for metabolite profiling from complex biological matrices.

Reading the Texture of Reality : Chaos Theory, Literature and the Humanist Perspective

Tutkimuksessa analysoidaan kaaosteorian vaikutusta kaunokirjallisuudessa ja kirjallisuudentutkimuksessa ja esitetään, että kaaosteorian roolia kirjallisuuden kentällä voidaan parhaiten ymmärtää sen avaamien käsitteiden kautta. Suoran soveltamisen sijaan kaaosteorian avulla on käyty uudenlaisia keskusteluja vanhoista aiheista ja luonnontieteestä ammennetut käsitteet ovat johtaneet aiemmin tukkeutuneiden argumenttien avaamiseen uudesta näkökulmasta käsin. Väitöskirjassa keskitytään kolmeen osa-alueeseen: kaunokirjallisen teoksen rakenteen teoretisointiin, ihmisen (erityisesti tekijän) identiteetin hahmottamiseen ja kuvailemiseen sekä fiktion ja todellisuuden suhteen pohdintaan. Tutkimuksen tarkoituksena on osoittaa, kuinka kaaosteorian kautta näitä aiheita on lähestytty niin kirjallisuustieteessä kuin kaunokirjallisissa teoksissakin. Väitöskirjan keskiössä ovat romaanikirjailija John Barthin, dramatisti Tom Stoppardin ja runoilija Jorie Grahamin teosten analyysit. Nämä kirjailijat ammentavat kaaosteoriasta keinoja käsitteellistää rakenteita, jotka ovat yhtä aikaa dynaamisia prosesseja ja hahmotettavia muotoja. Kaunokirjallisina teemoina nousevat esiin myös ihmisen paradoksaalisesti tunnistettava ja aina muuttuva identiteetti sekä lopullista haltuunottoa pakeneva, mutta silti kiehtova ja tavoiteltava todellisuus. Näiden kirjailijoiden teosten analyysin sekä teoreettisen keskustelun kautta väitöskirjassa tuodaan esiin aiemmassa tutkimuksessa varjoon jäänyt, koherenssia, ymmärrettävyyttä ja realismia painottava humanistinen näkökulma kaaosteorian merkityksestä kirjallisuudessa.

Karl Popper's Philosophy of Science - And the Evolution of the Popperian Worlds

This doctoral thesis in theoretical philosophy is a systematic analysis of Karl Popper's philosophy of science and its relation to his theory of three worlds. The general aim is to study Popper's philosophy of science and to show that Popper's theory of three worlds was a restatement of his earlier positions. As a result, a new reading of Popper's philosophy and development is offered and the theory of three worlds is analysed in a new manner. It is suggested that the theory of three worlds is not purely an ontological theory, but has a profound epistemological motivation. In Part One, Popper's epistemology and philosophy of science is analysed. It is claimed that Popper's thinking was bifurcated: he held two profound positions without noticing the tension between them. Popper adopted the position called the theorist around 1930 and focused on the logical structure of scientific theories. In Logik der Forschung (1935), he attempted to build a logic of science on the grounds that scientific theories may be regarded as universal statements which are not verifiable but can be falsified. Later, Popper emphasized another position, called here the processionalist. Popper focused on the study of science as a process and held that a) philosophy of science should study the growth of knowledge and that b) all cognitive processes are constitutive. Moreover, the constitutive idea that we see the world in the searchlight of our theories was combined with the biological insight that knowledge grows by trial and error. In Part Two, the theory of three worlds is analysed systematically. The theory is discussed as a cluster of theories which originate from Popper's attempt to solve some internal problems in his thinking. Popper adhered to realism and wished to reconcile the theorist and the processionalist. He also stressed the real and active nature of the human mind, and the possibility of objective knowledge. Finally, he wished to create a scientific world view.

First record of Nematospora coryli in Australia and its association with dry rot of Citrus

Nematospora (Eremothecium) coryli was isolated from Citrus and identified for the first time in Australia. This insect-transmitted yeast was associated with dry rot in cultivated and native Citrus fruits. Although N. coryli is known as a serious seed pathogen of many tropical and sub-tropical plants, evidence is presented that it has been present and undetected in Queensland for at least ninety years.

Truth, Proof and Gödelian Arguments : A Defence of Tarskian Truth in Mathematics

One of the most fundamental questions in the philosophy of mathematics concerns the relation between truth and formal proof. The position according to which the two concepts are the same is called deflationism, and the opposing viewpoint substantialism. In an important result of mathematical logic, Kurt Gödel proved in his first incompleteness theorem that all consistent formal systems containing arithmetic include sentences that can neither be proved nor disproved within that system. However, such undecidable Gödel sentences can be established to be true once we expand the formal system with Alfred Tarski s semantical theory of truth, as shown by Stewart Shapiro and Jeffrey Ketland in their semantical arguments for the substantiality of truth. According to them, in Gödel sentences we have an explicit case of true but unprovable sentences, and hence deflationism is refuted. Against that, Neil Tennant has shown that instead of Tarskian truth we can expand the formal system with a soundness principle, according to which all provable sentences are assertable, and the assertability of Gödel sentences follows. This way, the relevant question is not whether we can establish the truth of Gödel sentences, but whether Tarskian truth is a more plausible expansion than a soundness principle. In this work I will argue that this problem is best approached once we think of mathematics as the full human phenomenon, and not just consisting of formal systems. When pre-formal mathematical thinking is included in our account, we see that Tarskian truth is in fact not an expansion at all. I claim that what proof is to formal mathematics, truth is to pre-formal thinking, and the Tarskian account of semantical truth mirrors this relation accurately. However, the introduction of pre-formal mathematics is vulnerable to the deflationist counterargument that while existing in practice, pre-formal thinking could still be philosophically superfluous if it does not refer to anything objective. Against this, I argue that all truly deflationist philosophical theories lead to arbitrariness of mathematics. In all other philosophical accounts of mathematics there is room for a reference of the pre-formal mathematics, and the expansion of Tarkian truth can be made naturally. Hence, if we reject the arbitrariness of mathematics, I argue in this work, we must accept the substantiality of truth. Related subjects such as neo-Fregeanism will also be covered, and shown not to change the need for Tarskian truth. The only remaining route for the deflationist is to change the underlying logic so that our formal languages can include their own truth predicates, which Tarski showed to be impossible for classical first-order languages. With such logics we would have no need to expand the formal systems, and the above argument would fail. From the alternative approaches, in this work I focus mostly on the Independence Friendly (IF) logic of Jaakko Hintikka and Gabriel Sandu. Hintikka has claimed that an IF language can include its own adequate truth predicate. I argue that while this is indeed the case, we cannot recognize the truth predicate as such within the same IF language, and the need for Tarskian truth remains. In addition to IF logic, also second-order logic and Saul Kripke s approach using Kleenean logic will be shown to fail in a similar fashion.

Many-body effects in electrochemisorption : Part IV. Multi-boson formalism

Several boson subsystems may be involved in electrosorption phenomena. To accommodate this possibility, the one-boson formalism described in Parts I–III is extended to this case. The hierarchy in the superoperator scheme, the evaluation of operator averages for closure and several special cases are indicated. As an illustration, some calculations are presented to indicate the trends of many-body corrections in chemisorption.

Metabolism of 1,8-Cineole in Rat: Its Effects on Liver and Lung Microsomal Cytochrome P-450 Systems

The monoterpene cyclic ether, cineole (l,8-cineole, I) also known as eucalyptol, is a component of many essential oils and is widely distributed in nature. It is extensively used in pharmaceutical preparations for external application and also as a nasal spray. It was reported earlier that cineole when administered to sheep may be largely oxidized in the system (Scheline 1978). However the mode of metabolism of cineole is not known. Hence the present study was undertaken to investigate the metabolic fate of this ubiquitous terpenoid following its administration to rats by gastric intubation.

Gene expression profiling of cuticular proteins across the moult cycle of the crab Portunus pelagicus

Background: Crustaceans represent an attractive model to study biomineralization and cuticle matrix formation, as these events are precisely timed to occur at certain stages of the moult cycle. Moulting, the process by which crustaceans shed their exoskeleton, involves the partial breakdown of the old exoskeleton and the synthesis of a new cuticle. This cuticle is subdivided into layers, some of which become calcified while others remain uncalcified. The cuticle matrix consists of many different proteins that confer the physical properties, such as pliability, of the exoskeleton. Results: We have used a custom cDNA microarray chip, developed for the blue swimmer crab Portunus pelagicus, to generate expression profiles of genes involved in exoskeletal formation across the moult cycle. A total of 21 distinct moult-cycle related differentially expressed transcripts representing crustacean cuticular proteins were isolated. Of these, 13 contained copies of the cuticle_1 domain previously isolated from calcified regions of the crustacean exoskeleton, four transcripts contained a chitin_bind_4 domain (RR consensus sequence) associated with both the calcified and un-calcified cuticle of crustaceans, and four transcripts contained an unannotated domain (PfamB_109992) previously isolated from C. pagurus. Additionally, cryptocyanin, a hemolymph protein involved in cuticle synthesis and structural integrity, also displays differential expression related to the moult cycle. Moult stage-specific expression analysis of these transcripts revealed that differential gene expression occurs both among transcripts containing the same domain and among transcripts containing different domains. Conclusion: The large variety of genes associated with cuticle formation, and their differential expression across the crustacean moult cycle, point to the complexity of the processes associated with cuticle formation and hardening. This study provides a molecular entry path into the investigation of the gene networks associated with cuticle formation.

Photodimerization of coumarin in aqueous and micellar media

The photochemical and photophysical processes of many organic compounds are a function of the environment in which they are present. In this connection we have chosen to investigate the environmental perturbations on the photodimerization of coumarin,l and the results of our study in aqueous and micellar media are presented in this paper. Coumarin has historically been the subject of intense photochemical and spectroscopic interest, mainly as a consequence of its importance in biological systems. Coumarin has been chosen for our investigation as its fascinating photochemical behavior has been fairly well explored,2 and therefore the environmental influence, which is the subject of our concern, would be easily understandable.