"Kyl mä varmaan kohta ymmärrän." : Asunnon suunnittelu -opetusohjelma oppilaiden ajattelun ja oppimisen haastajana peruskoulun kotitalousopetuksessa

"I will soon understand." The House Planning Program as an Enhancer of Pupils´ Thinking Skills and Learning in Home Economics at Comprehensive School The aim of the research was to build a study program for home economics education in order to enhance pupils´ thinking skills. The program was based on the intervention programs or strategies known as Cognitive Acceleration (CA), which are founded on the theories of Jean Piaget, Lev Vygotsky, and Reuven Feuerstein. In addition, Carl Bereiter s theory of knowledge building was integrated to the research. The viewpoint of home economics was based on the multidimensional foundation of home economics science, particularly household technology and house planning. I first analyzed the kind of body of knowledge home economics science and home economics education provides for enhancing thinking skills in home economics. For the study, a CATE (Cognitive Acceleration through Technology Education) program was adapted and modified and a House Planning program was created for home economics classes. The house planning program consisted of five lessons during which pupils learned how to make functional floor plans as well as choose furniture, household appliances and materials for the home. In order to obtain the required data, various classroom experiments were arranged in 2005 with grade 9 pupils at a comprehensive school in Helsinki. All the experiments were videotaped, and five hours of the videotaped material was edited and transcribed for closer examination. The material consisted of all the video-recorded activity of the selected study group. Interaction study and content analysis were used to analyze the data. Following the experiments, a small survey was conducted to solicit pupils´ and teacher´s opinions of the program. The analysis sheds light on the nature of pupils´ interaction and knowledge building in small group activity. Special attention was given to tracking pupils´ interaction during the socalled construction zone activity. The models and qualities of teacher´s aid and support during the lessons were examined as well. The results revealed the versatility of the pupils social interaction and common knowledge building that occurred during the small group activity. The pupils discussions, including their arguments, their sharing of ideas, and the multiple perspectives that emerged reflected home economics knowledge building. The construction zone activity appeared through expressions of cognitive conflict and metacognition. Cognitive conflict was evident in the pupils´ words and involved questioning, doubting and disputing. The metacognitive activity emerged by thinking aloud, choosing the strategies, and negotiating the results. The pupils also coordinated their activity, allocated the responsibility, and systematized their work. The teacher assisted by preparing new themes for the pupils and by participating in the small group work. The teacher´s help during the small group sessions strengthened the pupils activity in the construction zone. The results showed that one can utilize the wide multidisciplinary basis of home economics, which includes scientific knowledge but also the knowledge derived from practical activity and experience. In this study practical activity was undertaken as a planning project the result of which was a plan or a new vision for the house planning situation. The study showed that the House Planning program was able to enhance the pupils´ social interaction and collaboration. The learning environment challenged the pupils in a way that could be a gateway to further developing their thinking skills. The method of analysis created in the study could be a potential tool for examining social interaction, construction zone activity, and knowledge building in other learning environments as well. Key words: home economics, house planning, classroom experiment, thinking skills,cognitive conflict, metacognition, social interaction, knowledge building

Early Growth and Later Health, Focus on Metabolic Syndrome, Obesity and Physical Activity

The Developmental Origins of Health and Disease Hypothesis proposes that adverse health outcomes in adult life are in part programmed during fetal life and infancy. This means that e.g. restricted nutrition during pregnancy programmes the offspring to store fat more effectively, to develop faster and to reach puberty earlier. These adaptations are beneficial in terms of short term survival. However, in developed countries these adaptations often lead to an increased risk of obesity and metabolic disturbances in later life, due to a mismatch between the prenatal and postnatal environment. This thesis aimed to study the role of early growth in people who are obese as adults, but metabolically healthy as well as in those who are normal in weight but metabolically obese. Other study aims were to assess whether physical activity and cardiorespiratory fitness are programmed early in life. The role of socioeconomic status in the development of obesity from a life course setting was also studied. These studies included 2003 men and women born in Helsinki between 1934 and 1944 with detailed information of their prenatal and childhood growth as well as living conditions. They participated in the detailed clinical examination during the years 2001-2004. A sub-group of the subjects participated in the UKK Institute 2-kilometre walk test. Metabolic syndrome was defined according to the 2005 criteria of the International Diabetes Federation. Among the obese men and women 20 % were metabolically healthy. Those with metabolic syndrome did not differ in birth size compared to the healthy ones, but by two years of age, they were lighter and thinner, and remained so up to 11 years. The period when changes in BMIs were predictive of the metabolic syndrome was from birth to 7 years. Of the normal weight individuals 17 % were metabolically obese. Again, there were no differences in birth size. However, by the age 7 years, those men who later developed metabolic syndrome were thinner. Gains in BMI during the first two years of life were protective of the syndrome. Children who were heavier, and especially taller, were more physically active, exercised with higher intensity and had higher cardiorespiratory fitness in their adult life than those who were shorter and thinner as children. Lower educational attainment and lower adult social class were associated with obesity in both men and women. Childhood social class was inversely associated with body mass index only in men while lower household income was associated with higher BMI in women. These results support the role of early life factors in the development of metabolic syndrome and adult life style. Early detection of risk factors predisposing to these conditions is highly relevant from a public health point of view.

Constructing a Community : Myths and Realities of the Open Development Model

The open development model of software production has been characterized as the future model of knowledge production and distributed work. Open development model refers to publicly available source code ensured by an open source license, and the extensive and varied distributed participation of volunteers enabled by the Internet. Contemporary spokesmen of open source communities and academics view open source development as a new form of volunteer work activity characterized by hacker ethic and bazaar governance . The development of the Linux operating system is perhaps the best know example of such an open source project. It started as an effort by a user-developer and grew quickly into a large project with hundreds of user-developer as contributors. However, in hybrids , in which firms participate in open source projects oriented towards end-users, it seems that most users do not write code. The OpenOffice.org project, initiated by Sun Microsystems, in this study represents such a project. In addition, the Finnish public sector ICT decision-making concerning open source use is studied. The purpose is to explore the assumptions, theories and myths related to the open development model by analysing the discursive construction of the OpenOffice.org community: its developers, users and management. The qualitative study aims at shedding light on the dynamics and challenges of community construction and maintenance, and related power relations in hybrid open source, by asking two main research questions: How is the structure and membership constellation of the community, specifically the relation between developers and users linguistically constructed in hybrid open development? What characterizes Internet-mediated virtual communities and how can they be defined? How do they differ from hierarchical forms of knowledge production on one hand and from traditional volunteer communities on the other? The study utilizes sociological, psychological and anthropological concepts of community for understanding the connection between the real and the imaginary in so-called virtual open source communities. Intermediary methodological and analytical concepts are borrowed from discourse and rhetorical theories. A discursive-rhetorical approach is offered as a methodological toolkit for studying texts and writing in Internet communities. The empirical chapters approach the problem of community and its membership from four complementary points of views. The data comprises mailing list discussion, personal interviews, web page writings, email exchanges, field notes and other historical documents. The four viewpoints are: 1) the community as conceived by volunteers 2) the individual contributor s attachment to the project 3) public sector organizations as users of open source 4) the community as articulated by the community manager. I arrive at four conclusions concerning my empirical studies (1-4) and two general conclusions (5-6). 1) Sun Microsystems and OpenOffice.org Groupware volunteers failed in developing necessary and sufficient open code and open dialogue to ensure collaboration thus splitting the Groupware community into volunteers we and the firm them . 2) Instead of separating intrinsic and extrinsic motivations, I find that volunteers unique patterns of motivations are tied to changing objects and personal histories prior and during participation in the OpenOffice.org Lingucomponent project. Rather than seeing volunteers as a unified community, they can be better understood as independent entrepreneurs in search of a collaborative community . The boundaries between work and hobby are blurred and shifting, thus questioning the usefulness of the concept of volunteer . 3) The public sector ICT discourse portrays a dilemma and tension between the freedom to choose, use and develop one s desktop in the spirit of open source on one hand and the striving for better desktop control and maintenance by IT staff and user advocates, on the other. The link between the global OpenOffice.org community and the local end-user practices are weak and mediated by the problematic IT staff-(end)user relationship. 4) Authoring community can be seen as a new hybrid open source community-type of managerial practice. The ambiguous concept of community is a powerful strategic tool for orienting towards multiple real and imaginary audiences as evidenced in the global membership rhetoric. 5) The changing and contradictory discourses of this study show a change in the conceptual system and developer-user relationship of the open development model. This change is characterized as a movement from hacker ethic and bazaar governance to more professionally and strategically regulated community. 6) Community is simultaneously real and imagined, and can be characterized as a runaway community . Discursive-action can be seen as a specific type of online open source engagement. Hierarchies and structures are created through discursive acts. Key words: Open Source Software, open development model, community, motivation, discourse, rhetoric, developer, user, end-user

Molecular methods for the epidemiological analysis of methicillin-resistant Staphylococcus aureus (MRSA) and Streptococcus pneumoniae

Methicillin-resistant Staphylococcus aureus (MRSA) and Streptococcus pneumoniae are major health problems worldwide, both found in symptomless carriage but also causing even life-threatening infections. The aim of this thesis was to characterise MRSA and S. pneumoniae in detail by using several molecular typing methods for various epidemiological purposes: clonality analysis, epidemiological surveillance, outbreak investigation, and virulence factor analysis. The characteristics of MRSA isolates from the strain collection of the Finnish National Infectious Disease Register (NIDR) and pneumococcal isolates collected from military recruits and children with acute otitis media (AOM) were analysed using various typing techniques. Antimicrobial susceptibility testing, pulsed-field gel electrophoresis (PFGE), multilocus sequence typing (MLST), spa typing, staphylococcal cassette chromosome mec (SCCmec) typing, and the detection of Panton-Valentine leukocidin (PVL) genes were performed for MRSA isolates. Pneumococcal isolates were analysed using antimicrobial susceptibility testing, serotyping, MLST, and by detecting pilus islet 1 (PI-1) and 2 (PI-2) genes. Several international community- and hospital-associated MRSA clones were recognised in Finland. The genetic diversity among MRSA FIN-4 isolates and among FIN-16 isolates was low. Overall, MRSA blood isolates from 1997 to 2006 were genetically diverse. spa typing was found to be a highly discriminatory, rapid and accurate typing method and it also qualifies as the primary typing method in countries with a long history of PFGE-based MRSA strain nomenclature. However, additional typing by another method, e.g. PFGE, is needed in certain situations to be able to provide adequate discrimination for epidemiological surveillance and outbreak investigation. An outbreak of pneumonia was associated with one pneumococcal strain among military recruits, previously healthy young men living in a crowded setting. The pneumococcal carriage rate after the outbreak was found to be exceptionally high. PI-1 genes were detected at a rather low prevalence among pneumococcal isolates from children with AOM. However, the study demonstrated that PI-1 has existed among pneumococcal isolates prior to pneumococcal conjugate vaccine and the increased antimicrobial resistance era. Moreover, PI-1 was found to associate with the serotype rather than the genotype. This study adds to our understanding of the molecular epidemiology of MRSA strains in Finland and the importance of an appropriate genotyping method to be able to perform high-level laboratory-based surveillance of MRSA. Epidemiological and molecular analyses of S. pneumoniae add to our knowledge of the characteristics of pneumococcal strains in Finland.

Interest in university studies : Its role and relation to other motivational variables

This dissertation empirically explored interest as a motivational force in university studies, including the role it currently plays and possible ways of enhancing this role as a student motivator. The general research questions were as follows: 1) What role does interest play in university studies? 2) What explains academic success if studying is not based on interest? 3) How do different learning environments support or impede interest-based studying? Four empirical studies addressed these questions. Study 1 (n=536) compared first-year students explanations of their disciplinary choices in three fields: veterinary medicine, humanities and law. Study 2 (n=28) focused on the role of individual interest in the humanities and veterinary medicine, fields which are very different from each other as regards their nature of studying. Study 3 (n=52) explored veterinary students motivation and study practices in relation to their study success. Study 4 (n=16) explored veterinary students interest experience in individual lectures on a daily basis. By comparing different fields and focusing on one study field in more detail, it was possible to obtain a many-sided picture of the role of interest in different learning environments. Questionnaires and quantitative methods have often been used to measure interest in academic learning. The present work is based mostly on qualitative data, and qualitative methods were applied to add to the previous research. Study 1 explored students open-ended answers, and these provided a basis for the interviews in Study 2. Study 3 explored veterinary students portfolios in a longitudinal setting. For Study 4, a diary including both qualitative and quantitative measures was designed to capture veterinary students interest experience. Qualitative content analysis was applied in all four studies, but quantitative analyses were also added. The thesis showed that university students often explain their disciplinary choices in terms of interest. Because interest is related to high-quality learning, the students seemed to have a good foundation for successful studies. However, the learning environments did not always support interest-based studying; Time-management and coping skills were found to be more important than interest in terms of study success. The results also indicated that interest is not the only motivational variable behind university studies. For example, future goals are needed in order to complete a degree. Even so, the results clearly indicated that it would be worth supporting interest-based studying both in professionally and generally oriented study fields. This support is important not only to promote high-quality learning but also meaningful studying, student well-being, and life-long learning.

Nonlinear hydrodynamics of a hard-sphere fluid near the glass transition

We conduct a numerical study of the dynamic behavior of a dense hard-sphere fluid by deriving and integrating a set of Langevin equations. The statics of the system is described by a free-energy functional of the Ramakrishnan-Yussouff form. We find that the system exhibits glassy behavior as evidenced through a stretched exponential decay and a two-stage relaxation of the density correlation function. The characteristic times grow with increasing density according to the Vogel-Fulcher law. The wave-number dependence of the kinetics is extensively explored. The connection of our results with experiment, mode-coupling theory, and molecular-dynamics results is discussed.

Precarious Pregnancies : Alcohol, drugs and the regulation of risks

Since the 1970s alcohol and drug use by pregnant women has become a target of political, professional and personal concern. The present study focuses on prenatal substance use and the regulation of risks by examining different kinds of societal responses to prenatal alcohol and drug use. The study analyses face-to-face encounters between professionals and service users at a specialised maternity clinic for pregnant women with substance abuse problems, medical and political discourses on the compulsory treatment of pregnant women as a means of FAS prevention and official recommendations on alcohol intake during pregnancy. Moreover, the study addresses the women s perspective by asking how women who have used illicit drugs during pregnancy perceive and rank the dangers linked to drug use. The study consists of five empirical sub-studies and a summary article. Sub-study I was written in collaboration with Dorte Hecksher and Sub-study IV with Riikka Perälä. Theoretically the study builds on the one hand, on the socio-cultural approach to the selection and perception of risks and on the other on governmentality studies which focus on the use of power in contemporary Western societies. The study is based on an ethnographic approach and makes use of the principles of multi-sited ethnography. The empirical sub-studies are based on three different types of qualitative data: ethnographic field notes from a maternity clinic from a period of 7 months, documentary material (medical journals, political documents, health education materials, government reports) and 3) interviews from maternity clinics with clients and members of staff. The study demonstrates that the logic of the regulation of prenatal alcohol use in Finland is characterised by the rise of the foetus , a process in which the urgency of protecting the foetus has gradually gained a more prominent role in the discourses on alcohol-related foetal damage. An increasing unwillingness to accept any kinds of risks when foetal health is at stake is manifested in the public debate on the compulsory treatment of pregnant women with alcohol problems and in the health authorities decision to advise pregnant women to refrain from alcohol use during pregnancy (Sub-studies I and II). Secondly, the study suggests that maternity care professionals have an ambivalent role in their mundane encounters with their pregnant clients: on the one hand professionals focus on the well-being of the foetus, but on the other, they need to take into account the women s needs and agency. The professionals daily encounters with their clients are thus characterised by hybridisation: the simultaneous use of technologies of domination and technologies of agency (Sub-studies III and IV). Finally, the study draws attention to the women s understanding of the risks of illicit drug during pregnancy, and shows that the women s understanding of risk differs from the bio-medical view. The study suggests that when drug-using pregnant women seek professional help they can feel that their moral worth is threatened by professionals negative attitudes which can make service-use challenging.

Linguistic and perceptual processing of communicative cues in Asperger Syndrome

Asperger Syndrome (AS) belongs to autism spectrum disorders where both verbal and non-verbal communication difficulties are at the core of the impairment. Social communication requires a complex use of affective, linguistic-cognitive and perceptual processes. In the four studies included in the current thesis, some of the linguistic and perceptual factors that are important for face-to-face communication were studied using behavioural methods. In all four studies the results obtained from individuals with AS were compared with typically developed age, gender and IQ matched controls. First, the language skills of school-aged children were characterized in detail with standardized tests that measured different aspects of receptive and expressive language (Study I). The children with AS were found to be worse than the controls in following complex verbal instructions. Next, the visual perception of facial expressions of emotion with varying degrees of visual detail was examined (Study II). Adults with AS were found to have impaired recognition of facial expressions on the basis of very low spatial frequencies which are important for processing global information. Following that, multisensory perception was investigated by looking at audiovisual speech perception (Studies III and IV). Adults with AS were found to perceive audiovisual speech qualitatively differently from typically developed adults, although both groups were equally accurate in recognizing auditory and visual speech presented alone. Finally, the effect of attention on audiovisual speech perception was studied by registering eye gaze behaviour (Study III) and by studying the voluntary control of visual attention (Study IV). The groups did not differ in eye gaze behaviour or in the voluntary control of visual attention. The results of the study series demonstrate that many factors underpinning face-to-face social communication are atypical in AS. In contrast with previous assumptions about intact language abilities, the current results show that children with AS have difficulties in understanding complex verbal instructions. Furthermore, the study makes clear that deviations in the perception of global features in faces expressing emotions as well as in the multisensory perception of speech are likely to harm face-to-face social communication.

Elämää keskustassa ja kaupunkiseudun reunoilla. Urbaani ja jälkiesikaupungillinen elämäntyyli asumisen valinnoissa ja arkiliikkumisessa Helsingin seudulla.

The lifestyles of people living in single-family housing areas on the outskirts of the Greater Helsinki Region (GHR) are different from those living in inner city area. The urban structure of the GHR is concentrated in the capital on the one hand, and spread out across the outskirts on the other. Socioeconomic spatial divisions are evident as well-paid and educated residents move to the inner city or the single-family house dominated suburban neighbourhoods depending on their housing preferences and life situations. The following thesis explores how these lifestyles have emerged through the housing choices and daily mobility of the residents living in the new single-family housing areas on the outskirts of the GHR and the inner city. The study shows that, when it comes to lifestyles, residents on the outskirts of the region have different housing preferences and daily mobility patterns when compared with their inner city counterparts. Based on five different case study areas my results show that these differences are related to residents values, preferences and attitudes towards the neighbourhood, on the one hand, and limited by urban structure on the other. This also confirms earlier theoretical analyses and findings from the GHR. Residents who moved to the outskirts of Greater Helsinki Region and the apartment buildings of the inner city were similar in the basic elements of their housing preferences: they sought a safe and peaceful neighbourhood close to the natural environment. However, where housing choices, daily mobility and activities vary different lifestyles develop in both the outskirts and the inner city. More specifically, lifestyles in the city apartment blocks were inherently urban. Liveliness and highest order facilities were appreciated and daily mobility patterns were supported by diverse modes of transportation for the purposes of work, shopping and leisure time. On the outskirts, by contrast, lifestyles were largely post-suburban and child-friendliness appreciated. Due to the heterachical urban structure, daily mobility was more car-dependent since work, shopping and free time activities of the residents are more spread around the region. The urban structure frames the daily mobility on the outskirts of the region, but this is not to say that short local trips replace longer regional ones. This comparative case study was carried out in the single-family housing areas of Sundsberg in Kirkkonummi, Landbo in Helsinki and Ylästö in Vantaa, as well as in the inner city apartment building areas of Punavuori and Katajanokka in Helsinki. The data is comprised of residential surveys, interviews, and statistics and GIS data sets that illustrate regional daily mobility, socio-economic structure and vis-à-vis housing stock.

Dietary habits and obesity: the role of emotional and cognitive factors

In post-industrialised societies, food is more plentiful, accessible and palatable than ever before and technological development has reduced the need for physical activity. Consequently, the prevalence of obesity is increasing, which is problematic as obesity is related to a number of diseases. Various psychological and social factors have an important influence on dietary habits and the development of obesity in the current food-rich and sedentary environments. The present study concentrates on the associations of emotional and cognitive factors with dietary intake and obesity as well as on the role these factors play in socioeconomic disparities in diet. Many people cognitively restrict their food intake to prevent weight gain or to lose weight, but research on whether restrained eating is a useful weight control strategy has produced conflicting findings. With respect to emotional factors, the evidence is accumulating that depressive symptoms are related to less healthy dietary intake and obesity, but the mechanisms explaining these associations remain unclear. Furthermore, it is not fully understood why socioeconomically disadvantaged individuals tend to have unhealthier dietary habits and the motives underlying food choices (e.g., price and health) could be relevant in this respect. The specific aims of the study were to examine 1) whether obesity status and dieting history moderate the associations of restrained eating with overeating tendencies, self-control and obesity indicators; 2) whether the associations of depressive symptoms with unhealthier dietary intake and obesity are attributable to a tendency for emotional eating and a low level of physical activity self-efficacy; and 3) whether the absolute or relative importance of food choice motives (health, pleasure, convenience, price, familiarity and ethicality) contribute to the socioeconomic disparities in dietary habits. The study was based on a large population-based sample of Finnish adults: the participants were men (N=2325) and women (N=2699) aged 25-74 who took part in the DILGOM (Dietary, Lifestyle and Genetic Determinants of Obesity and Metabolic Syndrome) sub-study of the National FINRISK Study 2007. The participants weight, height, waist circumference and body fat percentage were measured in a health examination. Psychological eating styles (the Three-Factor Eating Questionnaire-R18), food choice motives (a shortened version of the Food Choice Questionnaire), depressive symptoms (the Center for Epidemiological Studies Depression Scale) and self-control (the Brief Self-Control Scale) were measured with pre-existing questionnaires. A validated food frequency questionnaire was used to assess the average consumption of sweet and non-sweet energy-dense foods and vegetables/fruit. Self-reported total years of education and gross household income were used as indicators of socioeconomic position. The results indicated that 1) restrained eating was related to a lower body mass index, waist circumference, emotional eating and uncontrolled eating, and to a higher self-control in obese participants and current/past dieters. In contrast, the associations were the opposite in normal weight individuals and those who had never dieted. Thus, restrained eating may be related to better weight control among obese individuals and those with dieting experiences, while among others it may function as an indicator of problems with eating and an attempt to solve them. 2) Emotional eating and depressive symptoms were both related to less healthy dietary intake, and the greater consumption of energy-dense sweet foods among participants with elevated depressive symptoms was attributable to the susceptibility for emotional eating. In addition, emotional eating and physical activity self-efficacy were both important in explaining the positive association between depressive symptoms and obesity. 3) The lower vegetable/fruit intake and higher energy-dense food intake among individuals with a low socioeconomic position were partly explained by the higher priority they placed on price and familiarity and the lower priority they gave to health motives in their daily food choices. In conclusion, although policy interventions to change the obesogenic nature of the current environment are definitely needed, knowledge of the factors that hinder or facilitate people s ability to cope with the food-rich environment is also necessary. This study implies that more emphasis should be placed on various psychological and social factors in weight control programmes and interventions.

Synthesis and structures of oxyanion encapsulated copper(I)-dppm complexes (dppm = bis(diphenylphosphino) methane)

Copper(I)-dppm complexes encapsulating the oxyanions ClO4-, NO3-, CH3C6H4CO2-, SO42-, and WO42- have been synthesized either by reduction of the corresponding Cu(II) salts and treatment with dppm, or by treating the complex [Cu-2(dppm)(2)(dmcn)(3)](BF4)(2) (1) (dmcn = dimethyl cyanamide) with the respective anion. The isolated complexes [Cu-2(dppm)(2)(dmcn)(2)(ClO4)] (ClO4) (2), [Cu-2(dppm)(2)(dmcn)(2)(NO3)] (NO3) (3), Cu-2(dppm)(2)(NO3)(2) (4), [Cu-2(dppm)(2)(CH3C6H4CO2)(2)]dmcn.2THF (5), Cu-2(dppm)(2)(SO4) (6), and [Cu-3(dppm)(3)(Cl)(WO4)] 0.5H(2)O (7) have been characterized by IR, H-1 and P-31{H-1} NMR, UV-vis, and emission spectroscopy. The solid-state molecular structure of complexes 1, 2, 4, and 7 were determined by single-crystal X-ray diffraction. Pertinent crystal data are as follows: for 1, monoclinic P2(1)/c, a = 11.376(10) Angstrom, b = 42.503(7) Angstrom, c = 13.530(6) Angstrom, beta = 108.08(2)degrees, V = 6219(3) Angstrom(3), Z = 4; for 2, monoclinic P2(1)/c, a = 21.600(3) Angstrom, b = 12.968(3) Angstrom, c = 23.050(3) Angstrom, beta = 115.97(2)degrees, V = 5804(17) Angstrom(3), Z = 4; for 4, triclinic , a = 10.560(4) Angstrom, b = 10.553(3) Angstrom, c = 22.698(3) Angstrom, alpha = 96.08(2)degrees, beta = 96.03(2)degrees, gamma = 108.31(2)degrees, V = 2362(12) Angstrom(3), Z = 2; and for 7, orthorhombic P2(1)2(1)2(1), a = 14.407(4) Angstrom, b = 20.573(7) Angstrom, c = 24.176(6) Angstrom, V = 7166(4) Angstrom(3), Z = 4. Analyses of the crystallographic and spectroscopic data of these complexes reveal the nature of interactions between the Cu-I-dppm core and oxyanion. The anchoring of the oxyanion to the Cu-n(dppm)(n) unit is primarily through coordination to the metal, but the noncovalent C-H ... O interactions between the methylene and phenyl protons of the dppm and oxygen atoms of the oxyanion play a significant role. The solid-state emission spectra for complexes 1-6 are very similar but different from 7. In CDCl3 solution, addition of ClO4- or NO3- (as their tetrabutylammonium salts) to 1 establishes a rapid equilibrium between the anion-complexed and uncomplexed forms. The association constant values for ClO4- and NO3- have been estimated from the P-31{H-1} NMR spectra.

PocketAlign A Novel Algorithm for Aligning Binding Sites in Protein Structures

A fundamental task in bioinformatics involves a transfer of knowledge from one protein molecule onto another by way of recognizing similarities. Such similarities are obtained at different levels, that of sequence, whole fold, or important substructures. Comparison of binding sites is important to understand functional similarities among the proteins and also to understand drug cross-reactivities. Current methods in literature have their own merits and demerits, warranting exploration of newer concepts and algorithms, especially for large-scale comparisons and for obtaining accurate residue-wise mappings. Here, we report the development of a new algorithm, PocketAlign, for obtaining structural superpositions of binding sites. The software is available as a web-service at http://proline.physicslisc.emetin/pocketalign/. The algorithm encodes shape descriptors in the form of geometric perspectives, supplemented by chemical group classification. The shape descriptor considers several perspectives with each residue as the focus and captures relative distribution of residues around it in a given site. Residue-wise pairings are computed by comparing the set of perspectives of the first site with that of the second, followed by a greedy approach that incrementally combines residue pairings into a mapping. The mappings in different frames are then evaluated by different metrics encoding the extent of alignment of individual geometric perspectives. Different initial seed alignments are computed, each subsequently extended by detecting consequential atomic alignments in a three-dimensional grid, and the best 500 stored in a database. Alignments are then ranked, and the top scoring alignments reported, which are then streamed into Pymol for visualization and analyses. The method is validated for accuracy and sensitivity and benchmarked against existing methods. An advantage of PocketAlign, as compared to some of the existing tools available for binding site comparison in literature, is that it explores different schemes for identifying an alignment thus has a better potential to capture similarities in ligand recognition abilities. PocketAlign, by finding a detailed alignment of a pair of sites, provides insights as to why two sites are similar and which set of residues and atoms contribute to the similarity.

Thermodynamic properties and phase boundaries of Co O solutions

The thermodynamic properties of liquid unsaturated Co--O solutions have been determined by electrochemical measurements using (Y sub 2 O sub 3 )ThO sub 2 as solid electrolyte. The cell can be represented as, Pt. MoO sub 2 + Mo | (Y sub 2 O sub 3 )ThO sub 2 | O sub Co , tungsten, Pt, Emf of the cell was measured as a function of oxygen concentration in liquid Co at 1798, 1873 and 1973K. Least-mean squares regression analysis of the experimental data gives for the free energy of solution of diatomic oxygen in liquid Co Delta G exp 0 sub O(Co) = --84935--7.61 T ( plus/minus 400) J/g-atom and self interaction parameter for oxygen epsilon exp O sub O = --97240/T + 40.52 ( plus/minus 1) where the standard state for O is an infinitely dilute solution in which the activity is equal to atomic percent. The present data are discussed in comparison with those reported in the literature and the phase diagram for the Co--O system. 18 ref.--AA.

Thermoluminescence response in gamma and UV irradiated Dy2O3 nanophosphor

Low temperature solution combustion method was employed to synthesize Dy2O3 nanophosphors using two different fuels (sugar and oxalyl dihydrazine (ODH)). Powder X-ray diffraction confirm pure cubic phase and the estimated particle size from Scherrer's method in sugar and ODH fuel was found to be 26 and 78 nm, respectively, and are in close agreement with those obtained using TEM and W-H plot analysis. SEM micrographs reveal porous, irregular shaped particles with large agglomeration in both the fuels. An optical band gap of 5.24 eV and 5.46 eV was observed for Dy2O3 for sugar and ODH fuels, respectively. The blueshift observed in sugar fuel is attributed to the particles size effect. Thermoluminescence (TL) response of cubic Dy2O3 nanophosphors prepared by both fuels was examined using gamma and UV radiations. The thermoluminescence of sugar used samples shows a single glow peak at 377 degrees C for 1-4 kGy gamma irradiations. When dose is increased to 5 kGy, two more shouldered peaks were observed at 245 and 310 degrees C. However, in TL of ODH used samples, a single glow peak at 376 degrees C was observed. It is observed that TL intensity is found to be more in sugar used samples. In UV irradiated samples a single glow peak at 365 degrees C was recorded in both the fuels with a little variation in TL intensity. The trapping parameters were estimated by different methods and the results are discussed. (C) 2012 Elsevier B.V. All rights reserved.