α-Pinene oxide and verbenol oxide isomerizations over heterogeneous catalysts

Terpenes are a valuable natural resource for the production of fine chemicals. Turpentine, obtained from biomass and also as a side product of softwood industry, is rich in monoterpenes such as α-pinene and β-pinene, which are widely used as raw materials in the synthesis of flavors, fragrances and pharmaceutical compounds. The rearrangement of their epoxides has been thoroughly studied in recent years, as a method to obtain compounds which are further used in the fine chemical industry. The industrially most desired products of α-pinene oxide isomerization are campholenic aldehyde and trans-carveol. Campholenic aldehyde is an intermediate for the manufacture of sandalwood-like fragrances such as santalol. Trans-carveol is an expensive constituent of the Valencia orange essence oil used in perfume bases and food flavor composition. Furthermore it has been found to exhibit chemoprevention of mammary carcinogenesis. A wide range of iron and ceria supported catalysts were prepared, characterized and tested for α-pinene oxide isomerization in order to selective synthesis of above mentioned products. The highest catalytic activity in the preparation of campholenic aldehyde over iron modified catalysts using toluene as a solvent at 70 °C (total conversion of α-pinene oxide with a selectivity of 66 % to the desired aldehyde) was achieved in the presence of Fe-MCM-41. Furthermore, Fe-MCM-41 catalyst was successfully regenerated without deterioration of catalytic activity and selectivity. The most active catalysts in the synthesis of trans-carveol from α-pinene oxide over iron and ceria modified catalysts in N,N-dimethylacetamide as a solvent at 140 °C (total conversion of α-pinene oxide with selectivity 43 % to trans-carveol) were Fe-Beta-300 and Ce-Si-MCM-41. These catalysts were further tested for an analogous reaction, namely verbenol oxide isomerization. Verbenone is another natural organic compound which can be found in a variety of plants or synthesized by allylic oxidation of α-pinene. An interesting product which is synthesized from verbenone is (1R,2R,6S)-3-methyl-6-(prop-1-en-2-yl)cyclohex-3-ene-1,2-diol. It has been discovered that this diol possesses potent anti-Parkinson activity. The most effective way leading to desired diol starts from verbenone and includes three stages: epoxidation of verbenone to verbenone oxide, reduction of verbenone oxide and subsequent isomerization of obtained verbenol oxide, which is analogous to isomerization of α-pinene oxide. In the research focused on the last step of these synthesis, high selectivity (82 %) to desired diol was achieved in the isomerization of verbenol oxide at a conversion level of 96 % in N,N-dimethylacetamide at 140 °C using iron modified zeolite, Fe-Beta-300. This reaction displayed surprisingly high selectivity, which has not been achieved yet. The possibility of the reuse of heterogeneous catalysts without activity loss was demonstrated.

Heterogeneous response of adipose tissue to cancer cachexia

Cancer cachexia causes disruption of lipid metabolism. Since it has been well established that the various adipose tissue depots demonstrate different responses to stimuli, we assessed the effect of cachexia on some biochemical and morphological parameters of adipocytes obtained from the mesenteric (MES), retroperitoneal (RPAT), and epididymal (EAT) adipose tissues of rats bearing Walker 256 carcinosarcoma, compared with controls. Relative weight and total fat content of tissues did not differ between tumor-bearing rats and controls, but fatty acid composition was modified by cachexia. Adipocyte dimensions were increased in MES and RPAT from tumor-bearing rats, but not in EAT, in relation to control. Ultrastructural alterations were observed in the adipocytes of tumor-bearing rat RPAT (membrane projections) and EAT (nuclear bodies).

Agent-based management systems for many-core platforms : rigorous design and efficient implementation

Due to various advantages such as flexibility, scalability and updatability, software intensive systems are increasingly embedded in everyday life. The constantly growing number of functions executed by these systems requires a high level of performance from the underlying platform. The main approach to incrementing performance has been the increase of operating frequency of a chip. However, this has led to the problem of power dissipation, which has shifted the focus of research to parallel and distributed computing. Parallel many-core platforms can provide the required level of computational power along with low power consumption. On the one hand, this enables parallel execution of highly intensive applications. With their computational power, these platforms are likely to be used in various application domains: from home use electronics (e.g., video processing) to complex critical control systems. On the other hand, the utilization of the resources has to be efficient in terms of performance and power consumption. However, the high level of on-chip integration results in the increase of the probability of various faults and creation of hotspots leading to thermal problems. Additionally, radiation, which is frequent in space but becomes an issue also at the ground level, can cause transient faults. This can eventually induce a faulty execution of applications. Therefore, it is crucial to develop methods that enable efficient as well as resilient execution of applications. The main objective of the thesis is to propose an approach to design agentbased systems for many-core platforms in a rigorous manner. When designing such a system, we explore and integrate various dynamic reconfiguration mechanisms into agents functionality. The use of these mechanisms enhances resilience of the underlying platform whilst maintaining performance at an acceptable level. The design of the system proceeds according to a formal refinement approach which allows us to ensure correct behaviour of the system with respect to postulated properties. To enable analysis of the proposed system in terms of area overhead as well as performance, we explore an approach, where the developed rigorous models are transformed into a high-level implementation language. Specifically, we investigate methods for deriving fault-free implementations from these models into, e.g., a hardware description language, namely VHDL.

p.F508del in a heterogeneous cystic fibrosis population from Minas Gerais, Brazil

Cystic fibrosis (CF) is the most common autosomal recessive disease of the Caucasian population. Among the various CF mutations, p.F508del is the most frequent, accounting for two-thirds of the global CF chromosomes, although showing great variability among populations. We have studied 115 unrelated CF patients from a mixed population of Minas Gerais (Brazil). To evaluate part of the DNA sequence of the cystic fibrosis transmembrane conductance regulator (CFTR) gene, blood DNA was obtained and PCR was performed using two pairs of primers that anneal to exons 10 and 24 of the CFTR gene. The PCR product was then submitted to automatic sequencing using the ABI PRISM 310 Genetic Analyzer. The p.F508del mutation was found in 50 (21.7%) of 230 unrelated CF alleles. Fifteen (13.0%) patients were homozygous for this mutation, while 20 (17.4%) were heterozygous; the remaining 80 (69.6%) patients did not carry the p.F508del mutation. Exon 24 sequence had no change in 75 (65.2%) patients, 21 (18.3%) had the sequence variation 4521G/A, 11 (9.6%) had a not yet described sequence variation 4407T/A and 8 (7.0%) patients had both sequence variations (4521G/A and 4407T/A). The polymorphism 4407T/A results in an amino acid modification from aspartic acid to glutamic acid, which will probably have no function effect in CFTR. This low p.F508del prevalence can be due to the variable ethnic origin of this population from Minas Gerais, which may have a high diversity of CF rare mutations.

Liposomal photosensitizers: potential platforms for anticancer photodynamic therapy

Photodynamic therapy is a well-established and clinically approved treatment for several types of cancer. Antineoplastic photodynamic therapy is based on photosensitizers, i.e., drugs that absorb photons translating light energy into a chemical potential that damages tumor tissues. Despite the encouraging clinical results with the approved photosensitizers available today, the prolonged skin phototoxicity, poor selectivity for diseased tissues, hydrophobic nature, and extended retention in the host organism shown by these drugs have stimulated researchers to develop new formulations for photodynamic therapy. In this context, due to their amphiphilic characteristic (compatibility with both hydrophobic and hydrophilic substances), liposomes have proven to be suitable carriers for photosensitizers, improving the photophysical properties of the photosensitizers. Moreover, as nanostructured drug delivery systems, liposomes improve the efficiency and safety of antineoplastic photodynamic therapy, mainly by the classical phenomenon of extended permeation and retention. Therefore, the association of photosensitizers with liposomes has been extensively studied. In this review, both current knowledge and future perspectives on liposomal carriers for antineoplastic photodynamic therapy are critically discussed.

Embedded Service Bus for Internet of Things Interoperability

Internet of Things (IoT) technologies are developing rapidly, and therefore there exist several standards of interconnection protocols and platforms. The existence of heterogeneous protocols and platforms has become a critical challenge for IoT system developers. To mitigate this challenge, few alliances and organizations have taken the initiative to build a framework that helps to integrate application silos. Some of these frameworks focus only on a specific domain like home automation. However, the resource constraints in the large proportion of connected devices make it difficult to build an interoperable system using such frameworks. Therefore, a general purpose, lightweight interoperability framework that can be used for a range of devices is required. To tackle the heterogeneous nature, this work introduces an embedded, distributed and lightweight service bus, Lightweight IoT Service bus Architecture (LISA), which fits inside the network stack of a small real-time operating system for constrained nodes. LISA provides a uniform application programming interface for an IoT system on a range of devices with variable resource constraints. It hides platform and protocol variations underneath it, thus facilitating interoperability in IoT implementations. LISA is inspired by the Network on Terminal Architecture, a service centric open architecture by Nokia Research Center. Unlike many other interoperability frameworks, LISA is designed specifically for resource constrained nodes and it provides essential features of a service bus for easy service oriented architecture implementation. The presented architecture utilizes an intermediate computing layer, a Fog layer, between the small nodes and the cloud, thereby facilitating the federation of constrained nodes into subnetworks. As a result of a modular and distributed design, the part of LISA running in the Fog layer handles the heavy lifting to assist the lightweight portion of LISA inside the resource constrained nodes. Furthermore, LISA introduces a new networking paradigm, Node Centric Networking, to route messages across protocol boundaries to facilitate interoperability. This thesis presents a concept implementation of the architecture and creates a foundation for future extension towards a comprehensive interoperability framework for IoT.

Power and Performance Management Strategies on NoC-Based Multicore Platforms, Using DVFS, Adaptive Algorithm and Task Parallelism

This work presents synopsis of efficient strategies used in power managements for achieving the most economical power and energy consumption in multicore systems, FPGA and NoC Platforms. In this work, a practical approach was taken, in an effort to validate the significance of the proposed Adaptive Power Management Algorithm (APMA), proposed for system developed, for this thesis project. This system comprise arithmetic and logic unit, up and down counters, adder, state machine and multiplexer. The essence of carrying this project firstly, is to develop a system that will be used for this power management project. Secondly, to perform area and power synopsis of the system on these various scalable technology platforms, UMC 90nm nanotechnology 1.2v, UMC 90nm nanotechnology 1.32v and UMC 0.18 μmNanotechnology 1.80v, in order to examine the difference in area and power consumption of the system on the platforms. Thirdly, to explore various strategies that can be used to reducing system’s power consumption and to propose an adaptive power management algorithm that can be used to reduce the power consumption of the system. The strategies introduced in this work comprise Dynamic Voltage Frequency Scaling (DVFS) and task parallelism. After the system development, it was run on FPGA board, basically NoC Platforms and on these various technology platforms UMC 90nm nanotechnology1.2v, UMC 90nm nanotechnology 1.32v and UMC180 nm nanotechnology 1.80v, the system synthesis was successfully accomplished, the simulated result analysis shows that the system meets all functional requirements, the power consumption and the area utilization were recorded and analyzed in chapter 7 of this work. This work extensively reviewed various strategies for managing power consumption which were quantitative research works by many researchers and companies, it's a mixture of study analysis and experimented lab works, it condensed and presents the whole basic concepts of power management strategy from quality technical papers.

Exploring knowledge worker motivation in autonomous and interdependent problem solving tasks on virtual platforms

The objective of this study is to understand why virtual knowledge workers conduct autonomous tasks and interdependent problem solving tasks on virtual platforms. The study is qualitative case study including three case organizations that tap the knowledge of expert networks, and utilize virtual platforms in the work processes. Research data includes 15 interviews, that is, five experts from each case company. According to the findings there are some specific characteristics in motivation to work on tasks on online platforms. Autonomy, self-improvement, meaningful tasks, knowledge sharing, time management, variety of contacts, and variety of tasks, and projects motivate virtual knowledge workers. Factors that may enhance individuals’ engagement to work on tasks are trust, security of continuous task flow and income, feedback, meaningful tasks and tasks that contribute to self-improvement, flexibility and effectiveness in time management, and virtual tools that support social interaction. The results also indicate that there are some differences in individuals’ motivation based on the tasks’ nature. That is, knowledge sharing and variety of contacts motivated experts who worked on interdependent problem solving tasks. Then again, autonomy and variety of tasks motivated experts who worked on autonomous tasks.

Factors of innovation creation within functional heterogeneous project teams Case study: ABB Group

The research topic of the work is: “Factors of innovation creation within functionally heterogeneous project teams”. The research question is “What are the factors of innovation creation within functionally heterogeneous project teams?” The subject of this research is to explore the teams of projects, aimed at creating innovations, and understand how innovation is generated through project team work within them in term of factors. In line with the purposes of this study, firstly, it was analyzed what factors of such teams’ work are affecting creating innovation positively and negatively on the base of chosen literature and a preliminary conceptional framework was formulated, and secondly, the research of the work of project teams in one of the divisions of ABB company has been done and other factors and interdependencies between them have been added to the conceptional framework. This final conceptional framework constitutes the essense of the work findings and can be used as a tool to analyze the innovation creation process in functionally heterogeneous project teams

Modelling ecological values in heterogeneous and dynamic landscapes with geospatial data

Our surrounding landscape is in a constantly dynamic state, but recently the rate of changes and their effects on the environment have considerably increased. In terms of the impact on nature, this development has not been entirely positive, but has rather caused a decline in valuable species, habitats, and general biodiversity. Regardless of recognizing the problem and its high importance, plans and actions of how to stop the detrimental development are largely lacking. This partly originates from a lack of genuine will, but is also due to difficulties in detecting many valuable landscape components and their consequent neglect. To support knowledge extraction, various digital environmental data sources may be of substantial help, but only if all the relevant background factors are known and the data is processed in a suitable way. This dissertation concentrates on detecting ecologically valuable landscape components by using geospatial data sources, and applies this knowledge to support spatial planning and management activities. In other words, the focus is on observing regionally valuable species, habitats, and biotopes with GIS and remote sensing data, using suitable methods for their analysis. Primary emphasis is given to the hemiboreal vegetation zone and the drastic decline in its semi-natural grasslands, which were created by a long trajectory of traditional grazing and management activities. However, the applied perspective is largely methodological, and allows for the application of the obtained results in various contexts. Models based on statistical dependencies and correlations of multiple variables, which are able to extract desired properties from a large mass of initial data, are emphasized in the dissertation. In addition, the papers included combine several data sets from different sources and dates together, with the aim of detecting a wider range of environmental characteristics, as well as pointing out their temporal dynamics. The results of the dissertation emphasise the multidimensionality and dynamics of landscapes, which need to be understood in order to be able to recognise their ecologically valuable components. This not only requires knowledge about the emergence of these components and an understanding of the used data, but also the need to focus the observations on minute details that are able to indicate the existence of fragmented and partly overlapping landscape targets. In addition, this pinpoints the fact that most of the existing classifications are too generalised as such to provide all the required details, but they can be utilized at various steps along a longer processing chain. The dissertation also emphases the importance of landscape history as an important factor, which both creates and preserves ecological values, and which sets an essential standpoint for understanding the present landscape characteristics. The obtained results are significant both in terms of preserving semi-natural grasslands, as well as general methodological development, giving support to science-based framework in order to evaluate ecological values and guide spatial planning.

The Bootstrap of Mean for Dependent Heterogeneous Arrays.

Presently, conditions ensuring the validity of bootstrap methods for the sample mean of (possibly heterogeneous) near epoch dependent (NED) functions of mixing processes are unknown. Here we establish the validity of the bootstrap in this context, extending the applicability of bootstrap methods to a class of processes broadly relevant for applications in economics and finance. Our results apply to two block bootstrap methods: the moving blocks bootstrap of Künsch ( 989) and Liu and Singh ( 992), and the stationary bootstrap of Politis and Romano ( 994). In particular, the consistency of the bootstrap variance estimator for the sample mean is shown to be robust against heteroskedasticity and dependence of unknown form. The first order asymptotic validity of the bootstrap approximation to the actual distribution of the sample mean is also established in this heterogeneous NED context.

Suppression of long-branch attraction artefacts in the animal phylogeny using a site-heterogeneous model

Affiliation: Département de Biochimie, Université de Montréal

Factors Underlying Heterogeneous Individual Growth in Macrobrachium rosenbergii and the Effect of Size Heterogeneity on Economic Feasibility of Farming in Kuttanad ( Kerala )

School of Industrial Fisheries, Cochin University of Science and Technology

Organic Synthesis Mediated by Heterogeneous Catalysts

Catalysis is a technologically important field which determines the quality of life in future. Catalyst research in pharmaceutical industry,fine chemical synthesis and emission control demands supported catalysts in bulk quantities.In the present work it was observed that clay supported catalysts mentioned in various chapters could also be used for the synthesis of similar molecules. The K10Ti catalyst can be used for the synthesis similar substituted imidazole derivatives under solvent free conditions and synthetically important Mannich bases of substrates containing various substitutes.Al-pillared saponite can be used for acetalation of other polyhydroxy compounds like glycerol,mannitol etc.Cu-Pd KSF catalyst has found application in C-C bond forming reactions which can be applied to other reactions and similar methods can be adopted for the synthesis of other catalyst by changing the transition metals. Montmorillonite K10 catalysed synthesis of triarylpyridines can be extended to the synthesis tetrasubstuted pyroles.K10Ti can also be utilized for the synthesis of similar heterocycles.