Instabilities in electrochemical systems with a rotating disc electrode

Polarization curves experimentally obtained in the electro-dissolution of iron in a 1 M H2SO4 solution using a rotating disc as the working electrode present a current instability region within the range of applied voltage in which the current is controlled by mass transport in the electrolyte. According to the literature (Barcia et. al., 1992) the electro-dissolution process leads to the existence of a viscosity gradient in the interface metal-solution, which leads to a velocity field quantitatively different form the one developed in uniform viscosity conditions and may affect the stability of the hydrodynamic field. The purpose of this work is to investigate whether a steady viscosity profile, depending on the distance to the electrode surface, affects the stability properties of the classic velocity field near a rotating disc. Two classes of perturbations are considered: perturbations monotonically varying along the radial direction, and perturbations periodically modulated along the radial direction. The results show that the hydrodynamic field is always stable with respect to the first class of perturbations and that the neutral stability curves are modified by the presence of a viscosity gradient in the second case, in the sense of reducing the critical Reynolds number beyond which perturbations are amplified. This result supports the hypothesis that the current oscillations observed in the polarization curve may originate from a hydrodynamic instability.

On state and parameter estimation in chaotic systems

State-of-the-art predictions of atmospheric states rely on large-scale numerical models of chaotic systems. This dissertation studies numerical methods for state and parameter estimation in such systems. The motivation comes from weather and climate models and a methodological perspective is adopted. The dissertation comprises three sections: state estimation, parameter estimation and chemical data assimilation with real atmospheric satellite data. In the state estimation part of this dissertation, a new filtering technique based on a combination of ensemble and variational Kalman filtering approaches, is presented, experimented and discussed. This new filter is developed for large-scale Kalman filtering applications. In the parameter estimation part, three different techniques for parameter estimation in chaotic systems are considered. The methods are studied using the parameterized Lorenz 95 system, which is a benchmark model for data assimilation. In addition, a dilemma related to the uniqueness of weather and climate model closure parameters is discussed. In the data-oriented part of this dissertation, data from the Global Ozone Monitoring by Occultation of Stars (GOMOS) satellite instrument are considered and an alternative algorithm to retrieve atmospheric parameters from the measurements is presented. The validation study presents first global comparisons between two unique satellite-borne datasets of vertical profiles of nitrogen trioxide (NO3), retrieved using GOMOS and Stratospheric Aerosol and Gas Experiment III (SAGE III) satellite instruments. The GOMOS NO3 observations are also considered in a chemical state estimation study in order to retrieve stratospheric temperature profiles. The main result of this dissertation is the consideration of likelihood calculations via Kalman filtering outputs. The concept has previously been used together with stochastic differential equations and in time series analysis. In this work, the concept is applied to chaotic dynamical systems and used together with Markov chain Monte Carlo (MCMC) methods for statistical analysis. In particular, this methodology is advocated for use in numerical weather prediction (NWP) and climate model applications. In addition, the concept is shown to be useful in estimating the filter-specific parameters related, e.g., to model error covariance matrix parameters.

SELECTION OF HERBICIDES TARGETING THE USE IN CROP SYSTEMS CULTIVATED WITH SHOWY CROTALARIA

ABSTRACT The increase in the area planted with Crotalaria spectabilishas occurred by several factors, highlighting the potential to reduce the nematodes, nitrogen fixation and the high production of biomass. By becoming a species sown as a crop, it is necessary to control the weeds that coexist with showy crotalaria. This change in the use of this crop creates the possibility of this specie becoming a weed. The aim of this study was to assess the potential use of herbicides applied in preemergence and postemergence of C.spectabilisfor different purposes (control of volunteer and selectivity plants). Three experiments were installed in a greenhouse (two with herbicides applied in preemergence - in soils with distinct textural categories; and one experiment with herbicides applied in postemergence). The results of the experiments with herbicides applied in preemergence showed that: amicarbazone, atrazine, diuron, metribuzin, prometryn, fomesafen and sulfentrazone showed effectiveness for control of C.spectabilis in clayey soil. Besides these, flumioxazin and isoxaflutole also showed potential to be used in the control of showy crotalaria in soils with loam texture. In relation to the postemergence herbicides, atrazine, diuron, prometryn, flumioxazin, fomesafen, lactofen, saflufenacil, amonio-glufosinate and glyphosate can be used aiming the chemical control of C.spectabilis. Herbicides chlorimuron-ethyl, diclosulan, imazethapyr, pyrithiobac-sodium, trifloxysulfuron-sodium, clomazone, pendimethalin, S-metolachlor and trifluralin applied in preemergence, and imazethapyr, pyrithiobac-sodium, flumiclorac, bentazon and clethodim applied in postemergence caused low levels of injury to C.spectabilis plants, making necessary the development of new searches to ensure the selectivity of these products.

Influence of surface functionalization on the behavior of silica nanoparticles in biological systems

Personalized nanomedicine has been shown to provide advantages over traditional clinical imaging, diagnosis, and conventional medical treatment. Using nanoparticles can enhance and clarify the clinical targeting and imaging, and lead them exactly to the place in the body that is the goal of treatment. At the same time, one can reduce the side effects that usually occur in the parts of the body that are not targets for treatment. Nanoparticles are of a size that can penetrate into cells. Their surface functionalization offers a way to increase their sensitivity when detecting target molecules. In addition, it increases the potential for flexibility in particle design, their therapeutic function, and variation possibilities in diagnostics. Mesoporous nanoparticles of amorphous silica have attractive physical and chemical characteristics such as particle morphology, controllable pore size, and high surface area and pore volume. Additionally, the surface functionalization of silica nanoparticles is relatively straightforward, which enables optimization of the interaction between the particles and the biological system. The main goal of this study was to prepare traceable and targetable silica nanoparticles for medical applications with a special focus on particle dispersion stability, biocompatibility, and targeting capabilities. Nanoparticle properties are highly particle-size dependent and a good dispersion stability is a prerequisite for active therapeutic and diagnostic agents. In the study it was shown that traceable streptavidin-conjugated silica nanoparticles which exhibit a good dispersibility could be obtained by the suitable choice of a proper surface functionalization route. Theranostic nanoparticles should exhibit sufficient hydrolytic stability to effectively carry the medicine to the target cells after which they should disintegrate and dissolve. Furthermore, the surface groups should stay at the particle surface until the particle has been internalized by the cell in order to optimize cell specificity. Model particles with fluorescently-labeled regions were tested in vitro using light microscopy and image processing technology, which allowed a detailed study of the disintegration and dissolution process. The study showed that nanoparticles degrade more slowly outside, as compared to inside the cell. The main advantage of theranostic agents is their successful targeting in vitro and in vivo. Non-porous nanoparticles using monoclonal antibodies as guiding ligands were tested in vitro in order to follow their targeting ability and internalization. In addition to the targeting that was found successful, a specific internalization route for the particles could be detected. In the last part of the study, the objective was to clarify the feasibility of traceable mesoporous silica nanoparticles, loaded with a hydrophobic cancer drug, being applied for targeted drug delivery in vitro and in vivo. Particles were provided with a small molecular targeting ligand. In the study a significantly higher therapeutic effect could be achieved with nanoparticles compared to free drug. The nanoparticles were biocompatible and stayed in the tumor for a longer time than a free medicine did, before being eliminated by renal excretion. Overall, the results showed that mesoporous silica nanoparticles are biocompatible, biodegradable drug carriers and that cell specificity can be achieved both in vitro and in vivo.

Decision making and decision support in service systems

This thesis is a literature study that develops a conceptual model of decision making and decision support in service systems. The study is related to the Ä-Logi, Intelligent Service Logic for Welfare Sector Services research project, and the objective of the study is to develop the necessary theoretical framework to enable further research based on the research project results and material. The study first examines the concepts of service and service systems, focusing on understanding the characteristics of service systems and their implications for decision making and decision support to provide the basis for the development of the conceptual model. Based on the identified service system characteristics, an integrated model of service systems is proposed that views service systems through a number of interrelated perspectives that each offer different, but complementary, implications on the nature of decision making and the requirements for decision support in service systems. Based on the model, it is proposed that different types of decision making contexts can be identified in service systems that may be dominated by different types of decision making processes and where different types of decision support may be required, depending on the characteristics of the decision making context and its decision making processes. The proposed conceptual model of decision making and decision support in service systems examines the characteristics of decision making contexts and processes in service systems, and their typical requirements for decision support. First, a characterization of different types of decision making contexts in service systems is proposed based on the Cynefin framework and the identified service system characteristics. Second, the nature of decision making processes in service systems is proposed to be dual, with both rational and naturalistic decision making processes existing in service systems, and having an important and complementary role in decision making in service systems. Finally, a characterization of typical requirements for decision support in service systems is proposed that examines the decision support requirements associated with different types of decision making processes in characteristically different types of decision making contexts. It is proposed that decision support for the decision making processes that are based on rational decision making can be based on organizational decision support models, while decision support for the decision making processes that are based on naturalistic decision making should be based on supporting the decision makers’ situation awareness and facilitating the development of their tacit knowledge of the system and its tasks. Based on the proposed conceptual model a further research process is proposed. The study additionally provides a number of new perspectives on the characteristics of service systems, and the nature of decision making and requirements for decision support in service systems that can potentially provide a basis for further discussion and research, and support the practice alike.

Motor Types Comparison Determining Efficiency in Pumping Systems

Pumping, fan and compressor systems consume most of the motor electricity power in both the industrial and services sectors. A variable speed drive brings relevant improvements in a fluid system leading to energy saving that further on can be translated into Mtons reduction of CO 2 emissions. Standards and regulations are being adopted for fluid handling systems to limit the less efficiency pumps out of the European market on the coming years and a greater potential in energy savings is dictated by the Energy Efficiency Index (EEI) requirements for the whole pumping system and integrated pumps. Electric motors also have an International Efficiency (IE) classification in order to introduce higher efficiency motors into the market. In this thesis, the applicability of mid-size common electric motor types to industrial pumping system took place comparing the motor efficiency characteristics with each other and by analyzing the effect of motor dimensioning on the pumping system and its impact in the energy consumption.

The Smiles rearrangement in hydrazidic systems and related syntheses /|nG. A. Pawelchak. -- 260 St. Catharines, Ont. : [s. n.],

This research was directed towards the investigation of the Smiles rearrangement in hydrazidic systems and the synthesis of related heterocyclic compounds. The work can be conveniently divided into two main sections. Section 1 of the thesis relates to the synthesis and examination of the O+N migration of phenoxy- derivatives of hydrazidic halides. In general, hydrazidic halides were found to react with 2-nitrophenol and 4-nitrophenol to give corresponding a-nitrophenoxy- compounds. These a-nitrophenoxy- compounds were found to rearrange in warm base to give the corresponding N-benzoyl compounds via a proposed five-membered transition state. Experiments conducted in styrene revealed no radical contribution to the rearrangement. Cross-over product analysis indicated the rearrangement as intramolecular and consistent with the Smiles rearrangement. The preparation of N-a-chlorobenzylidene-N'-2-nitrophenyl- -N'-(2,4-dibromophenyl)hydrazine from N-benzoyl-N'-2-nitrophenyl- N'-(2,4-dibromophenyl)hydrazine was accomplished using phosphorus oxychloride. Examination of this hydrazidic chloride indicated a marked decrease .in reactivity as compared to the N-a-chlorobenzylidene-N'-phenylhydrazine case. Section 2 concerns itself with the preparation of heterocyclic compounds using an analogy of the five-membered transition state present in the Smiles rearrangement of a substituted benzylidene derivatives A new preparation of 2,4-phenyl1,3,4- oxadiazol-S-one using N-benzoyl-N'-phenylhydrazine and ethyl thiochloroformate is reported. Two new preparations of N-a-thiobenzoyl-N'-(2,4-dibromophenylhydrazine are reported using sodium hydrosulfide in conjunction with N-a-bromobenzylidene-N'-(2,4-dibromophenyl)hydrazine in the first, and phosphorus pentasulfide with N-benzoylN'-( 2,4-dibromophenyl)hydrazine in the second. The latter is preferred due to the formation of a sulfide co-product in the former. Two preparations of 2-phenyl-4-(2,4-dibromophenyl)-1,3,4- thiadiazol-S-one are reported using N-thiobenzoyl-N'-(2,4-dibromophenyl) hydrazine and ethyl chloroformate and ethyl thiochloroformate Two rapid and easy preparations of 2-phenyl-4-(2,4-dibromophenyl)- 1,3,4-triazol-S-one are reported using ethyl chloroformate and ethyl thiochloroformate. Sodium cyanate in conjunction with a-aminobenzylidene-N'-(2,4-dibromophenyl)hydrazine also provided 2-phenyl-4-(2,4-dibromophenyl)-1,3,4-triazol-S-one Section 2 concludes with an examination of two possible mechanistic routes to the prepared heterocycles.

Finding the Open Spaces in Closed Systems: An Exploration of Critical Pedagogy with a Social Justice Directive in an Ontario Secondary School Classroom

This study examines the first experience of students, teachers, and an administrator in implementing a teacher-designed Leadership in Social Justice Program at a large urban Ontario secondary school. The program aimed to infuse a Freirean concept of critical pedagogical praxis (Freire, 1970/1993) in a grade 12 integrated educational experience with a social justice directive. Data were collected through two questionnaires and eight in-depth interviews. The data identified three areas of awareness that described ways in which student participants were impacted most profoundly (a) developing self-awareness, (b) understanding a new educational paradigm, and (c) finding a place in the world. The study found that the program was successful in highlighting the possibility for more meaningful education and engaged many students deeply; however, its success was limited by the lead teacher’s failure to fully grasp and implement tenets of Freirean critical pedagogy that involved the role of the teacher in pedagogical processes.

Effects and Modifications in In/Se and In/Sb Systems by Swift Heavy Ion Irradiation

Department of Physics, Cochin University of Science and Technology

Sulphur Chemistry in Mangrove Systems of Tropical Cochin Estuary

Sulphur is a non conservative major element and is the most active species in the redox processes in nature, especially in aquatic environment . The varying oxidative states from-2 to +6 make it possible to enter into many of the biogeochemical processes. Thus the history, present and future of the chemical composition and behaviour of the natural aquatic systems and sediments have footprints of the sulphur chemistry.Mangroves are considered to be the most productive, fishery supportive ecosystem operating in the intertidal regions. The interlinking of the mangroves with the sulphur chemistry is attempted here.

Information Discovery in Distributed Systems-A Novel Concept Based on Modelling of Information Elements

Sharing of information with those in need of it has always been an idealistic goal of networked environments. With the proliferation of computer networks, information is so widely distributed among systems, that it is imperative to have well-organized schemes for retrieval and also discovery. This thesis attempts to investigate the problems associated with such schemes and suggests a software architecture, which is aimed towards achieving a meaningful discovery. Usage of information elements as a modelling base for efficient information discovery in distributed systems is demonstrated with the aid of a novel conceptual entity called infotron.The investigations are focused on distributed systems and their associated problems. The study was directed towards identifying suitable software architecture and incorporating the same in an environment where information growth is phenomenal and a proper mechanism for carrying out information discovery becomes feasible. An empirical study undertaken with the aid of an election database of constituencies distributed geographically, provided the insights required. This is manifested in the Election Counting and Reporting Software (ECRS) System. ECRS system is a software system, which is essentially distributed in nature designed to prepare reports to district administrators about the election counting process and to generate other miscellaneous statutory reports.Most of the distributed systems of the nature of ECRS normally will possess a "fragile architecture" which would make them amenable to collapse, with the occurrence of minor faults. This is resolved with the help of the penta-tier architecture proposed, that contained five different technologies at different tiers of the architecture.The results of experiment conducted and its analysis show that such an architecture would help to maintain different components of the software intact in an impermeable manner from any internal or external faults. The architecture thus evolved needed a mechanism to support information processing and discovery. This necessitated the introduction of the noveI concept of infotrons. Further, when a computing machine has to perform any meaningful extraction of information, it is guided by what is termed an infotron dictionary.The other empirical study was to find out which of the two prominent markup languages namely HTML and XML, is best suited for the incorporation of infotrons. A comparative study of 200 documents in HTML and XML was undertaken. The result was in favor ofXML.The concept of infotron and that of infotron dictionary, which were developed, was applied to implement an Information Discovery System (IDS). IDS is essentially, a system, that starts with the infotron(s) supplied as clue(s), and results in brewing the information required to satisfy the need of the information discoverer by utilizing the documents available at its disposal (as information space). The various components of the system and their interaction follows the penta-tier architectural model and therefore can be considered fault-tolerant. IDS is generic in nature and therefore the characteristics and the specifications were drawn up accordingly. Many subsystems interacted with multiple infotron dictionaries that were maintained in the system.In order to demonstrate the working of the IDS and to discover the information without modification of a typical Library Information System (LIS), an Information Discovery in Library Information System (lDLIS) application was developed. IDLIS is essentially a wrapper for the LIS, which maintains all the databases of the library. The purpose was to demonstrate that the functionality of a legacy system could be enhanced with the augmentation of IDS leading to information discovery service. IDLIS demonstrates IDS in action. IDLIS proves that any legacy system could be augmented with IDS effectively to provide the additional functionality of information discovery service.Possible applications of IDS and scope for further research in the field are covered.

Studies on vibrio spp. in juveniles of penaeus indicus in culture systems

The present study is carried out to understand (i) the incidence and occurrence of species of Vibrio in different culture systems in and around Cochin, (ii) characteristics of vibrios isolates, their ecology including growth response to various hydrological parameters, sensitivity to about 40 antibiotics, and (iii) role of physico-chemical parameters in pathogenicity of vibrios, etc. and the results emerged from the investigations are important and encouraging for better understanding of the 'vibriosis' in the culture systems to develop remedial measures to control diseases. The Thesis begins with an “Introduction” followed by “A review of literature” on diseases of penaeid shrimps with particular reference to 'vibriosis' and “Material and methods” which details with the methods and procedures followed in the experiments and analyses of data. This Thesis consists of three chapters. Chapter Ideals with the incidence and ecology of Vibrio spp. in water, sediment and in juveniles of the Indian white prawn Penaeus indicus in the culture systems. In Chapter 2, characteristics of vibrio isolates including growth response to various levels oftemperature, salinity and pl 1, sensitivity to 40 antibiotics and minimal inhibitory concentration tests are detailed.e out-breaks. The Chapter 3 discusses the role of physico-chemical parameters in the incidence, seasonal abundance of Vibrio spp. and in 'vibriosis'. A summary of the whole work and list of references are also included at the end. This study gives a detailed information regarding the incidence and ecology of vibrios in the culture systems. their characteristics and pathogenicity

Studies on the universal parameters and onset of chaos in dissipative systems

It has become clear over the last few years that many deterministic dynamical systems described by simple but nonlinear equations with only a few variables can behave in an irregular or random fashion. This phenomenon, commonly called deterministic chaos, is essentially due to the fact that we cannot deal with infinitely precise numbers. In these systems trajectories emerging from nearby initial conditions diverge exponentially as time evolves)and therefore)any small error in the initial measurement spreads with time considerably, leading to unpredictable and chaotic behaviour The thesis work is mainly centered on the asymptotic behaviour of nonlinear and nonintegrable dissipative dynamical systems. It is found that completely deterministic nonlinear differential equations describing such systems can exhibit random or chaotic behaviour. Theoretical studies on this chaotic behaviour can enhance our understanding of various phenomena such as turbulence, nonlinear electronic circuits, erratic behaviour of heart and brain, fundamental molecular reactions involving DNA, meteorological phenomena, fluctuations in the cost of materials and so on. Chaos is studied mainly under two different approaches - the nature of the onset of chaos and the statistical description of the chaotic state.

Information discovery in distributed systems - A novel concept based on modelling of information elements

This thesis attempts to investigate the problems associated with such schemes and suggests a software architecture, which is aimed towards achieving a meaningful discovery. Usage of information elements as a modelling base for efficient information discovery in distributed systems is demonstrated with the aid of a novel conceptual entity called infotron. The investigations are focused on distributed systems and their associated problems. The study was directed towards identifying suitable software architecture and incorporating the same in an environment where information growth is phenomenal and a proper mechanism for carrying out information discovery becomes feasible. An empirical study undertaken with the aid of an election database of constituencies distributed geographically, provided the insights required. This is manifested in the Election Counting and Reporting Software (ECRS) System. ECRS system is a software system, which is essentially distributed in nature designed to prepare reports to district administrators about the election counting process and to generate other miscellaneous statutory reports.