Structural studies of analgesics and their interactions. VII. Stereoisomerism and disorder in the structure of oxyphenbutazone monohydrate

Oxyphenbutazone, C19H20N203, a metabolite and perhaps the active form of phenylbutazone, is a widely used non-narcotic analgesic and anti-inflammatory pyrazolidinedione derivative. The monohydrate of the compound crystallizes in the triclinic space group Pi with two molecules in a unit cell of dimensions a -- 9.491 (4), b = 10.261 (5), c = 11.036 (3)A and ¢~ = 72.2 (1), fl = 64.3 (1), 7 = 73.0 (1) °. The structure was solved by direct methods and refined to an R value of 0.107 for 1498 observed reflections. The butyl group in the molecule is disordered. The hydroxyl group occupies two sites with unequal occupancies. On account of the asymmetry at the two N atoms and one of the C atoms in the central five-membered ring, the molecule can exist in eight isomeric states, of which four are sterically unfavourable. The disorder in the position of the hydroxyl group can be readily explained on the basis of the existence, with unequal abundances, of all four sterically favourable isomers.The bond lengths and angles in the molecule are similar to those in phenylbutazone. The crystal structure is stabilized by van der Waals interactions, and O-H... O hydrogen bonds involving the carbonyl and the hydroxyl groups as well as a water molecule.

Kemian ylioppilaskokeen tehtävät summatiivisen arvioinnin välineenä

The main purpose of the research was to illustrate chemistry matriculation examination questions as a summative assessment tool, and represent how the questions have evolved over the years. Summative assessment and its various test item classifications, Finnish goal-oriented curriculum model, and Bloom’s Revised Taxonomy of Cognitive Objectives formed the theoretical framework for the research. The research data consisted of 257 chemistry questions from 28 matriculation examinations between 1996 and 2009. The analysed test questions were formulated according to the national upper secondary school chemistry curricula 1994, and 2003. Qualitative approach and theory-driven content analysis method were employed in the research. Peer review was used to guarantee the reliability of the results. The research was guided by the following questions: (a) What kinds of test item formats are used in chemistry matriculation examinations? (b) How the fundamentals of chemistry are included in the chemistry matriculation examination questions? (c) What kinds of cognitive knowledge and skills do the chemistry matriculation examination questions require? The research indicates that summative assessment was used diversely in chemistry matriculation examinations. The tests included various test item formats, and their combinations. The majority of the test questions were constructed-response items that were either verbal, quantitative, or experimental questions, symbol questions, or combinations of the aforementioned. The studied chemistry matriculation examinations seldom included selected-response items that can be either multiple-choice, alternate choice, or matching items. The relative emphasis of the test item formats differed slightly depending on whether the test was a part of an extensive general studies battery of tests in sciences and humanities, or a subject-specific test. The classification framework developed in the research can be applied in chemistry and science education, and also in educational research. Chemistry matriculation examinations are based on the goal-oriented curriculum model, and cover relatively well the fundamentals of chemistry included in the national curriculum. Most of the test questions related to the symbolism of chemical equation, inorganic and organic reaction types and applications, the bonding and spatial structure in organic compounds, and stoichiometry problems. Only a few questions related to electrolysis, polymers, or buffer solutions. None of the test questions related to composites. There were not any significant differences in the emphasis between the tests formulated according to the national curriculum 1994 or 2003. Chemistry matriculation examinations are cognitively demanding. The research shows that the majority of the test questions require higher-order cognitive skills. Most of the questions required analysis of procedural knowledge. The questions that only required remembering or processing metacognitive knowledge, were not included in the research data. The required knowledge and skill level varied slightly between the test questions in the extensive general studies battery of tests in sciences and humanities, and subject-specific tests administered since 2006. The proportion of the Finnish chemistry matriculation examination questions requiring higher-order cognitive knowledge and skills is very large compared to what is discussed in the research literature.

Thin-walled timber and FRP-timber veneer composite CEE-sections

This paper compares the structural performance between thin-walled timber and FRP-timber composite Cee-sections. While, thin-walled composite timber structures have been proven to be efficient and ultra-light structural elements, their manufacturing is difficult and labour intensive. Significant effort and time is required to prevent the cracking of the transverse timber veneers, bent in the grain direction, when forming the cross-sectional shape. FRP-timber structures overcome this disadvantage by replacing the transverse veneers with flexible, unidirectional FRP material and only keeping the timber veneers which are bent in their natural rolling direction. The Cee-sections investigated in this study were 210 mm deep × 90 mm wide × 500 mm high and manufactured from five plies. For both section types, the three internal plies were thin (1 mm thick) softwood Hoop pine (Araucaria cunninghamii) veneers, orientated along the section longitudinal axis. The two outer layers, providing bending stiffness to the walls, were Hoop pine veneers (1 mm thick) for the timber sections and glass fibre reinforced plastic (0.73 mm thick) for the FRP-timber sections orientated perpendicular to the inner layers. The manufacturing process is briefly introduced in this paper. The profiles were fitted with strain gauges and tested in compression. Linear Variable Displacement Transducers also recorded the buckling along one flange. The test results are presented and discussed in this paper in regards to their structural behaviour and performance. Results showed that the use of FRP in the sections increases both the elastic local buckling load and section capacity, the latter being increased by about 24 percent. The results indicate that thin-walled FRP-timber can ultimately be used as a sustainable alternative to cold-formed steel profiles.

Context-dependent mate choice in the sand goby, Pomatoschistus minutus

The results presented in this thesis show that all females of a given population do not necessarily choose similar mating partners. Specifically, partner preferences of a fish, the sand goby (Pomatoschistus minutus), varied among individual females and depended on the social context at the time of choice. I also show that females assess multiple mate choice cues simultaneously; partner preferences were based more strongly on an interaction effect between different choice cues than on any individual cue. Furthermore, I found that preferred matings involved fitness benefits in the form of increased offspring success, but these benefits were not significantly affected by mate compatibility. Hence, mate choice for partner compatibility does not appear to be an important determinant of the observed variation in female mate preferences in this species. The context-dependency of female mating preferences revealed is relevant to how genetic variation in sexually selected traits might be maintained: as the mating success of a certain male type varies according to the choice context, directional sexual selection on male traits is shown to be less intense than generally thought making for a slower loss of genetic variation in these traits. Mating preferences of sand gobies were assessed by giving females a binary choice between males that differed in body size and/or other focus traits. These association preferences were found to be sexually motivated, repeatable and to correspond to actual mating decisions.

Correlated Gaussian Sources over Orthogonal Gaussian Channels

We consider the transmission of correlated Gaussian sources over orthogonal Gaussian channels. It is shown that the Amplify and Forward (AF) scheme which simplifies the design of encoders and the decoder, performs close to the optimal scheme even at high SNR. Also, it outperforms a recently proposed scalar quantizer scheme both in performance and complexity. We also study AF when there is side information at the encoders and decoder.

Expected Performance of the ATLAS Experiment - Detector, Trigger and Physics

A detailed study is presented of the expected performance of the ATLAS detector. The reconstruction of tracks, leptons, photons, missing energy and jets is investigated, together with the performance of b-tagging and the trigger. The physics potential for a variety of interesting physics processes, within the Standard Model and beyond, is examined. The study comprises a series of notes based on simulations of the detector and physics processes, with particular emphasis given to the data expected from the first years of operation of the LHC at CERN.

Kehittämistutkimus: Tieto- ja viestintätekniikkaa kemian opetukseen

The main aim of the present study was to develop information and communication technology (ICT) based chemistry education. The goals for the study were to support meaningful chemistry learning, research-based teaching and diffusion of ICT innovations. These goals were used as guidelines that form the theoretical framework for this study. This Doctoral Dissertation is based on eight-stage research project that included three design researches. These three design researches were scrutinized as separate case studies in which the different cases were formed according to different design teams: i) one researcher was in charge of the design and teachers were involved in the research process, ii) a research group was in charge of the design and students were involved in the research process, and iii) the design was done by student teams, the research was done collaboratively, and the design process was coordinated by a researcher. The research projects were conducted using mixed method approach, which enabled a comprehensive view on education design. In addition, the three central areas of design research: problem analysis, design solution and design process were included in the research, which was guided by the main research questions formed according to these central areas: 1) design solution: what kind of elements are included in ICT-based learning environments that support meaningful chemistry learning and diffusion of innovation, 2) problem analysis: what kind of new possibilities the designed learning environments offer for the support of meaningful chemistry learning, and 3) design process: what kind of opportunities and challenges does collaboration bring to the design of ICT-based learning environments? The main research questions were answered according to the analysis of the survey and observation data, six designed learning environments and ten design narratives from the three case studies. Altogether 139 chemistry teachers and teacher students were involved in the design processes. The data was mainly analysed by methods of qualitative content analysis. The first main result from the study give new information on the meaningful chemistry learning and the elements of ICT-based learning environment that support the diffusion of innovation, which can help in the development of future ICT-education design. When the designed learning environment was examined in the context of chemistry education, it was evident that an ICT-based chemistry learning environment supporting the meaningful learning of chemistry motivates the students and makes the teacher s work easier. In addition, it should enable the simultaneous fulfilment of several pedagogical goals and activate higher-level cognitive processes. The learning environment supporting the diffusion of ICT innovation is suitable for Finnish school environment, based on open source code, and easy to use with quality chemistry content. According to the second main result, new information was acquired about the possibilities of ICT-based learning environments in supporting meaningful chemistry learning. This will help in setting the goals for future ICT education. After the analysis of design solutions and their evaluations, it can be said that ICT enables the recognition of all elements that define learning environments (i.e. didactic, physical, technological and social elements). The research particularly demonstrates the significance of ICT in supporting students motivation and higher-level cognitive processes as well as versatile visualization resources for chemistry that ICT makes possible. In addition, research-based teaching method supports well the diffusion of studied innovation on individual level. The third main result brought out new information on the significance of collaboration in design research, which guides the design of ICT education development. According to the analysis of design narratives, it can be said that collaboration is important in the execution of scientifically reliable design research. It enables comprehensive requirement analysis and multifaceted development, which improves the reliability and validity of the research. At the same time, it sets reliability challenges by complicating documenting and coordination, for example. In addition, a new method for design research was developed. Its aim is to support the execution of complicated collaborative design projects. To increase the reliability and validity of the research, a model theory was used. It enables time-pound documenting and visualization of design decisions that clarify the process. This improves the reliability of the research. The validity of the research is improved by requirement definition through models. This way learning environments that meet the design goals can be constructed. The designed method can be used in education development from comprehensive to higher level. It can be used to recognize the needs of different interest groups and individuals with regard to processes, technology and substance knowledge as well as interfaces and relations between them. The developed method has also commercial potential. It is used to design learning environments for national and international market.

Synthesis, characterization, EPR and thermoluminescence properties of CaTiO3 nanophosphor

Calcium titanate (CaTiO3) nanophosphors were synthesized by three different routes namely solution combustion (SC), modified solid-state reaction (MSS) and solid-state (SS) methods. Rietveld refinement studies revealed the presence of an orthorhombic structure with traces of CaCO3. The crystallite sizes were found to be in the 43-45 nm range. TEM studies also confirm the nano size with well crystalline nature. EPR spectrum for SS method exhibits a broad resonance signal at g = 2.027 is attributed to TiO6](9-) center, whereas in MSS sample the resonance signals are attributed to surface electron and hole trapping sites. The TL behavior has been investigated for the first time using gamma-irradiation. TL glow peak at 169 degrees C were recorded in CaTiO3 prepared by SC, MSS and SS methods. The trapping parameters such as activation energy (E) and order of kinetics (b) were estimated using peak shape method and results are discussed in detail. (C) 2013 Elsevier Ltd. All rights reserved.

Dependence of electron recombination time and light to electricity conversion efficiency on shape of the nanocrystal light sensitizer

Tunability of electron recombination time and light to electricity conversion efficiency to superior values in semiconductor sensitized solar cells via optimized design of nanocrystal light sensitizer shape is discussed here.

Interplay of structural distortions, dielectric effects and magnetic order in multiferroic GdMnO3

Multiferroic materials are characterized by simultaneous magnetic and ferroelectric ordering making them good candidates for magneto-electrical applications. We conducted thermal expansion and magnetostriction measurements in magnetic fields up to 14 T on perovskitic GdMnO3 by highresolution capacitive dilatometry in an effort to determine all longitudinal and transversal components of the magnetostriction tensor. Below the ordering temperature T (N) = 42 K, i.e., within the different complex (incommensurate or complex) antiferromagnetic phases, lattice distortions of up to 100 ppm have been found. Although no change of the lattice symmetry occurs, the measurements reveal strong magneto-structural phenomena, especially in the incommensurate sinusoidal antiferromagnetic phase. A strong anisotropy of the magnetoelastic properties was found, in good agreement with the type and propagation vector of the magnetic structure. We demonstrate that our capacitive dilatometry can detect lattice expansion effects and changes of the dielectric permittivity simultaneously because the sample is housed inside the capacitor. A separation of both effects is possible by shielding the sample. Dielectric transitions could be detected by this method and compared to the critical values of H and T in the magnetic phase diagram. Dielectric changes measured at 1 kHz excitation frequency are detected in GdMnO3 at about 180 K, and between 10 K and 25 K in the canted antiferromagnetic structure which is characterized by a complex magnetic order on both the Gd- and Mn-sites.

Antelope mating strategies facilitate invasion of grasslands by a woody weed

Intra and interspecific variation in frugivore behaviour can have important consequences for seed dispersal outcomes. However, most information comes from among-species comparisons, and within-species variation is relatively poorly understood. We examined how large intraspecific differences in the behaviour of a native disperser, blackbuck antelope Antilope cervicapra, influence dispersal of a woody invasive, Prosopis juliflora, in a grassland ecosystem. Blackbuck disperse P. juliflora seeds through their dung. In lekking blackbuck populations, males defend clustered or dispersed mating territories. Territorial male movement is restricted, and within their territories males defecate on dung-piles. In contrast, mixed-sex herds range over large areas and do not create dung-piles. We expected territorial males to shape seed dispersal patterns, and seed deposition and seedling recruitment to be spatially localized. Territorial males had a disproportionately large influence on seed dispersal. Adult males removed twice as much fruit as females, and seed arrival was disproportionately high on territories. Also, because lek-territories are clustered, seed arrival was spatially highly concentrated. Seedling recruitment was also substantially higher on territories compared with random sites, indicating that the local concentration of seeds created by territorial males continued into high local recruitment of seedlings. Territorial male behaviour may, thus, result in a distinct spatial pattern of invasion of grasslands by the woody P. juliflora. An ex situ experiment showed no beneficial effect of dung and a negative effect of light on seed germination. We conclude that large intraspecific behavioural differences within frugivore populations can result in significant variation in their effectiveness as seed dispersers. Mating strategies in a disperser could shape seed dispersal, seedling recruitment and potentially plant distribution patterns. These mating strategies may aid in the spread of invasives, such as P. juliflora, which could, in turn, negatively influence the behaviour and ecology of native dispersers.

A Mild Protocol for the Regioselective Ring Opening of Doubly Activated Cyclopropanes by Using Selenolates Generated in Situ: Synthesis of Functionalized Organoselenium Compounds

A variety of functionalized organoselenium compounds were synthesized from doubly activated cyclopropanes and diselenides in the presence of sodium borohydride. A range of substituents were stable under these reaction conditions. Additionally, we extended the scope of the method by reducing nitro groups in the products to give the corresponding selenium-containing unnatural amino acids.

On Locally Gabriel Geometric Graphs

Let be a set of points in the plane. A geometric graph on is said to be locally Gabriel if for every edge in , the Euclidean disk with the segment joining and as diameter does not contain any points of that are neighbors of or in . A locally Gabriel graph(LGG) is a generalization of Gabriel graph and is motivated by applications in wireless networks. Unlike a Gabriel graph, there is no unique LGG on a given point set since no edge in a LGG is necessarily included or excluded. Thus the edge set of the graph can be customized to optimize certain network parameters depending on the application. The unit distance graph(UDG), introduced by Erdos, is also a LGG. In this paper, we show the following combinatorial bounds on edge complexity and independent sets of LGG: (i) For any , there exists LGG with edges. This improves upon the previous best bound of . (ii) For various subclasses of convex point sets, we show tight linear bounds on the maximum edge complexity of LGG. (iii) For any LGG on any point set, there exists an independent set of size .