One-dimensional zig-zag type coordination polymers of Ni(II) and Cu(II) containing 1,3-benzenedicarboxylate and 1,3-diaminopropane: Structural, spectral and thermal studies

Two coordination polymers [Ni(ipt)(dap)(2)](n) (1) and [Cu(ipt)(dap)H2O](n) center dot nH(2)O (2) with an overall one-dimensional arrangement and having isophthalate (ipt) as bridging moieties and chelating 1,3-diaminopropane (dap) as structure modulating units have been prepared and characterized by crystallographic, spectroscopic and thermo-analytical studies. Both have an overall one-dimensional zig-zag nature but with a distorted octahedral NiN4O2 chromophore for 1 and a distorted square pyramidal CuN2O3 chromophore for 2. Even though the ipt units are acting as bridging units through mono-dentatively coordinating carboxylate functions in both polymers, compound 1 has the carboxylate oxygen linkages at the trans positions, while in 2 the oxygen linkages occur at the cis positions leading to a different type of zig-zag arrangement. Relevant spectral and bonding parameters also could be evaluated for the compounds using UV-Vis and EPR spectra. Thermal stability and possible structural modifications on thermal treatment of the compounds were also investigated and the relevant thermodynamic and kinetic parameters evaluated from the thermal data. (C) 2007 Elsevier B.V. All rights reserved.

Primordial Perturbations from a Self-interacting Curvaton

Inflation is a period of accelerated expansion in the very early universe, which has the appealing aspect that it can create primordial perturbations via quantum fluctuations. These primordial perturbations have been observed in the cosmic microwave background, and these perturbations also function as the seeds of all large-scale structure in the universe. Curvaton models are simple modifications of the standard inflationary paradigm, where inflation is driven by the energy density of the inflaton, but another field, the curvaton, is responsible for producing the primordial perturbations. The curvaton decays after inflation as ended, where the isocurvature perturbations of the curvaton are converted into adiabatic perturbations. Since the curvaton must decay, it must have some interactions. Additionally realistic curvaton models typically have some self-interactions. In this work we consider self-interacting curvaton models, where the self-interaction is a monomial in the potential, suppressed by the Planck scale, and thus the self-interaction is very weak. Nevertheless, since the self-interaction makes the equations of motion non-linear, it can modify the behaviour of the model very drastically. The most intriguing aspect of this behaviour is that the final properties of the perturbations become highly dependent on the initial values. Departures of Gaussian distribution are important observables of the primordial perturbations. Due to the non-linearity of the self-interacting curvaton model and its sensitivity to initial conditions, it can produce significant non-Gaussianity of the primordial perturbations. In this work we investigate the non-Gaussianity produced by the self-interacting curvaton, and demonstrate that the non-Gaussianity parameters do not obey the analytically derived approximate relations often cited in the literature. Furthermore we also consider a self-interacting curvaton with a mass in the TeV-scale. Motivated by realistic particle physics models such as the Minimally Supersymmetric Standard Model, we demonstrate that a curvaton model within the mass range can be responsible for the observed perturbations if it can decay late enough.

Governance theory as a framework for empirical research : a case study on local environmental policy-making in Helsinki, Finland

Governance has been one of the most popular buzzwords in recent political science. As with any term shared by numerous fields of research, as well as everyday language, governance is encumbered by a jungle of definitions and applications. This work elaborates on the concept of network governance. Network governance refers to complex policy-making situations, where a variety of public and private actors collaborate in order to produce and define policy. Governance is processes of autonomous, self-organizing networks of organizations exchanging information and deliberating. Network governance is a theoretical concept that corresponds to an empirical phenomenon. Often, this phenomenon is used to descirbe a historical development: governance is often used to describe changes in political processes of Western societies since the 1980s. In this work, empirical governance networks are used as an organizing framework, and the concepts of autonomy, self-organization and network structure are developed as tools for empirical analysis of any complex decision-making process. This work develops this framework and explores the governance networks in the case of environmental policy-making in the City of Helsinki, Finland. The crafting of a local ecological sustainability programme required support and knowledge from all sectors of administration, a number of entrepreneurs and companies and the inhabitants of Helsinki. The policy process relied explicitly on networking, with public and private actors collaborating to design policy instruments. Communication between individual organizations led to the development of network structures and patterns. This research analyses these patterns and their effects on policy choice, by applying the methods of social network analysis. A variety of social network analysis methods are used to uncover different features of the networked process. Links between individual network positions, network subgroup structures and macro-level network patterns are compared to the types of organizations involved and final policy instruments chosen. By using governance concepts to depict a policy process, the work aims to assess whether they contribute to models of policy-making. The conclusion is that the governance literature sheds light on events that would otherwise go unnoticed, or whose conceptualization would remain atheoretical. The framework of network governance should be in the toolkit of the policy analyst.

Non-periodic tilings in 2-dimensions with 4, 6, 8, 10 and 12-fold symmetries

The two dimensional plane can be filled with rhombuses, so as to generate non-periodic tilings with 4, 6, 8, 10 and 12-fold symmetries. Some representative tilings constructed using the rule of inflation are shown. The numerically computed diffraction patterns for the corresponding tilings are also shown to facilitate a comparison with possible X-ray or electron diffraction pictures.

As-deposited near-single crystalline high Tc and Jc superconducting thin films by a pulsed lased deposition process

As-deposited high Tc superconducting Y1Ba2Cu3O7−x films with zero resistance temperatures of similar, equals89 K and critical current densities about 0.7×106 A/cm2 at 77 K have been reproducibly fabricated at a substrate holder temperature at 650°C, using pulsed laser deposition, without post-annealing. One key to these results is the injection of gaseous oxygen into laser produced plume just in front of the target. In this way, the correct amount of oxygen is incorporated into the as-grown film so that post-deposition treatment becomes unnecessary. Axial ion channeling in these as-deposit high Tc superconducting films on (100) SrTiO3 and X-ray photoelectron spectroscopy (XPS) on the film surfaces were performed. Angular yield profile near the film surface for Ba, and the surface peak intensity were measured using 3 MeV He ions. For channeling normal to the substrate a minimum yield of 7%, compared to similar, equals3% for single crystals, was obtained. The results of ion channeling and XPS studies indicate that the as-deposited films have good crystallinity as well as toichiometry to within similar, equals1 nm of the film surface. The in-situ growth of such high Tc and Jc films is an important step in the use of the laser deposition technique to fabricate multilayer structures and the surface perfection is of importance in tunneling devices such as Josephson junctions.

Lectin Microarrays for Glycomic Analysis

Glycomics is the study of comprehensive structural elucidation and characterization of all glycoforms found in nature and their dynamic spatiotemporal changes that are associated with biological processes. Glycocalyx of mammalian cells actively participate in cell-cell, cell-matrix, and cell-pathogen interactions, which impact embryogenesis, growth and development, homeostasis, infection and immunity, signaling, malignancy, and metabolic disorders. Relative to genomics and proteomics, glycomics is just growing out of infancy with great potential in biomedicine for biomarker discovery, diagnosis, and treatment. However, the immense diversity and complexity of glycan structures and their multiple modes of interactions with proteins pose great challenges for development of analytical tools for delineating structure function relationships and understanding glycocode. Several tools are being developed for glycan profiling based on chromatography,m mass spectrometry, glycan microarrays, and glyco-informatics. Lectins, which have long been used in glyco-immunology, printed on a microarray provide a versatile platform for rapid high throughput analysis of glycoforms of biological samples. Herein, we summarize technological advances in lectin microarrays and critically review their impact on glycomics analysis. Challenges remain in terms of expansion to include nonplant derived lectins, standardization for routine clinical use, development of recombinant lectins, and exploration of plant kingdom for discovery of novel lectins.

European aspen and hybrid aspen under changing environment : Leaf traits, growth and litter decomposition

Understanding the responses of species and ecosystems to human-induced global environmental change has become a high research priority. The main aim of this thesis was to investigate how certain environmental factors that relate to global change affect European aspen (Populus tremula), a keystone species in boreal forests, and hybrid aspen (P. tremula × P. tremuloides), cultivated in commercial plantations. The main points under consideration were the acclimatization potential of aspen through changes in leaf morphology, as well as effects on growth, leaf litter chemistry and decomposition. The thesis is based on two experiments, in which young aspen (< 1 year) were exposed either to an atmospheric pollutant [elevated ozone (O3)] or variable resource availability [water, nitrogen (N)]; and two field studies, in which mature trees (> 8 years) were growing in environments exposed to multiple environmental stress factors (roadside and urban environments). The field studies included litter decomposition experiments. The results show that young aspen, especially the native European aspen, was sensitive to O3 in terms of visible leaf injuries. Elevated O3 resulted in reduced biomass allocation to roots and accelerated leaf senescence, suggesting negative effects on growth in the long term. Water and N availability modified the frost hardening of young aspen: High N supply, especially when combined with drought, postponed the development of frost hardiness, which in turn may predispose trees to early autumn frosts. This effect was more pronounced in European aspen. The field studies showed that mature aspen acclimatized to roadside and urban environments by producing more xeromorphic leaves. Leaf morphology was also observed to vary in response to interannual climatic variation, which further indicates the ability of aspen for phenotypic plasticity. Intraspecific variation was found in several of the traits measured, although intraspecific differences in response to the abiotic factors examined were generally small throughout the studies. However, some differences between clones were found in sensitivity to O3 and the roadside environment. Aspen leaf litter decomposition was retarded in the roadside environment, but only initially. By contrast, decomposition was found to be faster in the urban than the rural environment throughout the study. The higher quality of urban litter (higher in N, lower in lignin and phenolics), as well as higher temperature, N deposition and humus pH at the urban site were factors likely to promote decay. The phenotypic plasticity combined with intraspecific variation found in the studies imply that aspen has potential for withstanding environmental changes, although some global change factors, such as rising O3 levels, may adversely affect its performance. The results also suggest that the multiple environmental changes taking place in urban areas which correspond closely with the main drivers of global change can modify ecosystem functioning by promoting litter decomposition, mediated partly by alterations in leaf litter quality.

Optimization of sample preparation for next-generation sequencing with Illumina Genome Analyzer II

The growing interest for sequencing with higher throughput in the last decade has led to the development of new sequencing applications. This thesis concentrates on optimizing DNA library preparation for Illumina Genome Analyzer II sequencer. The library preparation steps that were optimized include fragmentation, PCR purification and quantification. DNA fragmentation was performed with focused sonication in different concentrations and durations. Two column based PCR purification method, gel matrix method and magnetic bead based method were compared. Quantitative PCR and gel electrophoresis in a chip were compared for DNA quantification. The magnetic bead purification was found to be the most efficient and flexible purification method. The fragmentation protocol was changed to produce longer fragments to be compatible with longer sequencing reads. Quantitative PCR correlates better with the cluster number and should thus be considered to be the default quantification method for sequencing. As a result of this study more data have been acquired from sequencing with lower costs and troubleshooting has become easier as qualification steps have been added to the protocol. New sequencing instruments and applications will create a demand for further optimizations in future.

Social networks for volunteered geographic information - A case study of OpenStreetMap

The world of mapping has changed. Earlier, only professional experts were responsible for map production, but today ordinary people without any training or experience can become map-makers. The number of online mapping sites, and the number of volunteer mappers has increased significantly. The development of the technology, such as satellite navigation systems, Web 2.0, broadband Internet connections, and smartphones, have had one of the key roles in enabling the rise of volunteered geographic information (VGI). As opening governmental data to public is a current topic in many countries, the opening of high quality geographical data has a central role in this study. The aim of this study is to investigate how is the quality of spatial data produced by volunteers by comparing it with the map data produced by public authorities, to follow what occurs when spatial data are opened for users, and to get acquainted with the user profile of these volunteer mappers. A central part of this study is OpenStreetMap project (OSM), which aim is to create a map of the entire world by volunteers. Anyone can become an OpenStreetMap contributor, and the data created by the volunteers are free to use for anyone without restricting copyrights or license charges. In this study OpenStreetMap is investigated from two viewpoints. In the first part of the study, the aim was to investigate the quality of volunteered geographic information. A pilot project was implemented by following what occurs when a high-resolution aerial imagery is released freely to the OpenStreetMap contributors. The quality of VGI was investigated by comparing the OSM datasets with the map data of The National Land Survey of Finland (NLS). The quality of OpenStreetMap data was investigated by inspecting the positional accuracy and the completeness of the road datasets, as well as the differences in the attribute datasets between the studied datasets. Also the OSM community was under analysis and the development of the map data of OpenStreetMap was investigated by visual analysis. The aim of the second part of the study was to analyse the user profile of OpenStreetMap contributors, and to investigate how the contributors act when collecting data and editing OpenStreetMap. The aim was also to investigate what motivates users to map and how is the quality of volunteered geographic information envisaged. The second part of the study was implemented by conducting a web inquiry to the OpenStreetMap contributors. The results of the study show that the quality of OpenStreetMap data compared with the data of National Land Survey of Finland can be defined as good. OpenStreetMap differs from the map of National Land Survey especially because of the amount of uncertainty, for example because of the completeness and uniformity of the map are not known. The results of the study reveal that opening spatial data increased notably the amount of the data in the study area, and both the positional accuracy and completeness improved significantly. The study confirms the earlier arguments that only few contributors have created the majority of the data in OpenStreetMap. The inquiry made for the OpenStreetMap users revealed that the data are most often collected by foot or by bicycle using GPS device, or by editing the map with the help of aerial imageries. According to the responses, the users take part to the OpenStreetMap project because they want to make maps better, and want to produce maps, which have information that is up-to-date and cannot be found from any other maps. Almost all of the users exploit the maps by themselves, most popular methods being downloading the map into a navigator or into a mobile device. The users regard the quality of OpenStreetMap as good, especially because of the up-to-dateness and the accuracy of the map.

Aluekehittämisverkostojen arviointi : Verkostotoimijanäkökulma MAL- ja hyvinvointiverkostoihin aluekehittämisen välineinä

The Finnish regional development system has gone through structural reforms from state centered governed system to multi-actor governance, based on negotiation and cooperation. One of the reforms has been the regional cohesion and competitiveness program (COCO) established in 2010. The aim of the program is to increase competitiveness through all the regions and balance the regional development by supporting networking. The main focus of the program is to improve the methods and tools for regional development. In the program there are seven thematic networks founded around topics seen important national wide. This thesis explores regional development networks and their evaluation COCO:s two thematic networks, Wellbeing and Land use, housing and transportation as examples. The aim of the thesis is to explore the network actors understanding of thematic networks as tools for regional development. In particular, the study focuses on how the actors see the possible network level outcomes and wider effects of the networking activity. In addition, the central themes of the study are the prerequisite for successful network processes and improvement of the network process effectiveness by evaluation. The research material in this study consist the interviews of the network coordinators and national and regional actors participating in the network activities. The interviews were conducted in spring 2011. Based on the research results, the networks act on national regional and network level and across them. The cooperation is based on official and unofficial relations. The structure of the networks seemed to be self-organizing and controlled at the same time. The structural elements were found to set the framework for the network process and evaluation. According to the results, the networks enabled the more effective operation of the national development system, support of the regions and political lobbying. For the regions the networks offered support for areal development, new resources and possibility to influence national discourse. As conclusion, the role of the network was to disseminate information, create possibilities for collaboration and execute projects and studies and to effect on national policy making. These factors determined the effectiveness of the networks. However, because different regions were satisfied with different network level outcomes, the utilization of the networks in the regions should be evaluated by their own objectives. Resources, motivation, competence and perceptions of the effects were found to affect the successful implementation of the network process and cooperation in networks. Some network level obstacles could be overcome with coordination, but the challenge was the ability and motivation of the areas to utilize the networks as resources and see them as part of the comprehensive development agenda. Thus, the development should focus on how to increase awareness on how to improve regional cooperation processes and how multiple regional actors could enhance their working by utilizing the networks.

Persistence Problem in Two-Dimensional Fluid Turbulence

We present a natural framework for studying the persistence problem in two-dimensional fluid turbulence by using the Okubo-Weiss parameter Lambda to distinguish between vortical and extensional regions. We then use a direct numerical simulation of the two-dimensional, incompressible Navier-Stokes equation with Ekman friction to study probability distribution functions (PDFs) of the persistence times of vortical and extensional regions by employing both Eulerian and Lagrangian measurements. We find that, in the Eulerian case, the persistence-time PDFs have exponential tails; by contrast, this PDF for Lagrangian particles, in vortical regions, has a power-law tail with an exponent theta = 2.9 +/- 0.2.

Deformation behaviour of commercially pure titanium at extreme strain rates

The evolution of microstructure and texture during room temperature compression of commercially pure Ti with four different initial orientations were studied under quasi-static and dynamic loading conditions. At a low strain rate (epsilon)over dot = 3 x 10(-4) s(-1) the different initial textures yielded the same end texture, despite different microstructural evolution in terms of twin boundaries. High strain rate deformation at (epsilon)over dot = 1.5 x 10(3) s(-1) was characterized by extensive twinning and evolution of a texture that was similar to that at low strain rate with minor differences. However, there was a significant difference in the strength of the texture for different orientations that was absent for low strain rate deformed samples at high strain rate. A viscoplastic self-consistent model with a secant approach was used to corroborate the experimental results by simulation. (C) 2011 Published by Elsevier Ltd. on behalf of Acta Materialia Inc.

A template-free, combustion-chemical route to macroporous nickel monoliths displaying a hierarchy of pore sizes

Recently, we demonstrated a very general route to monolithic macroporous materials prepared without the use of templates (Rajamathi et al. J. Mater. Chem. 2001, 11, 2489). The route involves finding a precursor containing two metals, A and B, whose oxides are largely immiscible. Firing of the precursor followed by suitable sintering results in a monolith from which one of the oxide phases can be chemically leached out to yield a macroporous mass of the other oxide phase. The metals A and B that we employed in the demonstration were Ni and Zn. From the NiO-ZnO monolith that was obtained by decomposing the precursor, ZnO could be leached out at high pH to yield macroporous NiO. In the present work, we show that combustion-chemical (also called self-propagating) decomposition of a mixture of Ni and Zn nitrates with urea as a fuel yields an intimate mixture of the oxides that can be sintered and leached with alkali to form a macroporous NiO monolith. The new process that we present here thereby avoids the need for a crystalline single-source precursor. A novel and unanticipated aspect of the present work is that the combination of high temperatures and rapid quenching associated with combustion synthesis results in an intimate mixture of wurtzite ZnO and the metastable rock-salt Ni1-xZnxO where x is about 0.3. Leaching this monolith with alkali gives a macroporous mass of rock-salt Ni1-xZnxO, which upon reduction in H-2/Ar forms macroporous Ni and ZnO. There are thus two stages in the process that lead to two modes of pore formation. The first is associated with leaching of ZnO by alkali. The second is associated with the reduction of porous Ni1-xZnxO to give porous Ni and ZnO.

Sandwich propellant combustion: Modeling and experimental comparison

This paper reports reacting fluid dynamics calculations for an ammonium percholrate binder sandwich and extracts experimentally observed features including surface profiles and maximum regression rates as a function of pressure and binder thickness. These studies have been carried out by solving the two-dimensional unsteady Navier-Stokes equations with energy and species conservation equations and a kinetic model of three reaction steps (ammonium perchlorate decomposition flame, primary diffusion flame, and final diffusion flame) in the gas phase. The unsteady two-dimensional conduction equation is solved in the condensed phase. The regressing surface is unsteady and two dimensional. Computations have been carried out for a binder thickness range of 25-125 mum and a pressure range of 1.4 to 6.9 MPa. Good comparisons at several levels of detail are used to demonstrate the need for condensed-phase two-dimensional unsteady conduction and three-step gas-phase reactions. The choice of kinetic and thermodynamic parameters is crucial to good comparison with experiments. The choice of activation energy parameters for ammonium percholrate combustion has been made with stability of combustion in addition to experimentally determined values reported in literature. The choice of gas-phase parameters for the diffusion flames are made considering that (a) primary diffusion flame affects the low-pressure behavior and (b) final diffusion flame affects high-pressure behavior. The predictions include the low-pressure deflagration limit of the sandwich apart from others noted above. Finally, this study demonstrates the possibility of making meaningful comparisons with experimental observations on sandwich propellant combustion.

Regimes of spray formation in gas-centered swirl coaxial atomizers

Spray formation in ambient atmosphere from gas-centered swirl coaxial atomizers is described by carrying out experiments in a spray test facility. The atomizer discharges a circular air jet and an axisymmetric swirling water sheet from its coaxially arranged inner and outer orifices. A high-speed digital imaging system along with a backlight illumination arrangement is employed to record the details of liquid sheet breakup and spray development. Spray regimes exhibiting different sheet breakup mechanisms are identified and their characteristic features presented. The identified spray regimes are wave-assisted sheet breakup, perforated sheet breakup, segmented sheet breakup, and pulsation spray regime. In the regime of wave-assisted sheet breakup, the sheet breakup shows features similar to the breakup of two-dimensional planar air-blasted liquid sheets. At high air-to-liquid momentum ratios, the interaction process between the axisymmetric swirling liquid sheet and the circular air jet develops spray processes which are more specific to the atomizer studied here. The spray exhibits a periodic ejection of liquid masses whose features are dominantly controlled by the central air jet.