Successive refinement of structures with data of increasing resolution: a theoretical study for triclinic space groups

The method of least squares could be used to refine an imperfectly related trial structure by adoption of one of the following two procedures: (i) using all the observed at one time or (ii) successive refinement in stages with data of increasing resolution. While the former procedure is successful in the case of trial structures which are sufficiently accurate, only the latter has been found to be successful when the mean positional error (i.e.<|[Delta]r|>) for the atoms in the trial structure is large. This paper makes a theoretical study of the variation of the R index, mean phase-angle error, etc. as a function of <|[Delta]r|> for data corresponding to different esolutions in order to find the best refinement procedure [i.e. (i) or (ii)] which could be successfully employed for refining trial structures in which <|[Delta]r|> has large, medium and low values. It is found that a trial structure for which the mean positional error is large could be refined only by the method of successive refinement with data of increasing resolution.

Bättre folk, bättre smak? : Suomenruotsalaisten maku ja kulttuuripääoma

The aim of my thesis, which consists of five original articles and a summarizing chapter, is to study the identity, lifestyle and cultural taste of the Finnish Swedes, i.e. the Swedish-speaking language minority in Finland, from a qualitative point of view. The Finnish Swedes are a somewhat special minority, first of all because of their wide-ranging language rights guaranteed by the constitution, and secondly because of the common image that Finnish Swedes represent a more legitimate or better lifestyle and taste than the Finnish-Speaking Finns. This conception is corroborated by the fact that, in comparison to the language majority, the Swedish-speakers have better health, employment, income and so on according to a number of quantitative studies. My research data is composed of twenty-six focus group interviews conducted among a geographically and socio-economically wide range of Swedish-speaking Finns. Group sizes ranged from 3 to 11 people. In the interviews, culture was approached through a framework of seven topics: music, cinema, television, arts, reading, eating and clothing. In each focus group interview, two subfields of culture were discussed along with a short section about cultural events and participation and definitions on good and bad taste. After discussing culture and taste, there was a final discussion on the Finnish Swede identity. The main theoretical framework of my thesis comes from Pierre Bourdieu (1979) and his followers: I am asking whether the status of being a Swedish-speaker can be used as a means of distinction. The main research questions are the following: (1) How does the Swedish-speaking minority look studied in the light of extensive qualitative data and in a framework of lifestyle and taste? (2) What kind of differences in lifestyle, taste and linguistic identity are there between different Finnish Swedes and how do those connect with socio-economical position, place of residence or age? I also ask how belonging to the language minority might work as a tool for cultural distinction and how different Swedish-speaking groups take use of it. My main research question is (3) whether mother tongue is a remarkable factor of lifestyle or cultural taste in contemporary Finland.

Directing role of functional groups in selective generation of C-H center dot center dot center dot pi interactions: In situ cryo-crystallographic studies on benzyl derivatives

The in situ cryo-crystallization study of benzyl derivatives reveals that the molecular packing in these compounds is either through methylene (sp(3)) C-H center dot center dot center dot pi or aromatic (sp(2)) C-H center dot center dot center dot pi interactions depending on the level of acidity of the benzyl proton. These studies of low melting compounds bring out the subtle features of such weak interactions and point to the directional preferences depending on the nature (electron withdrawing, polarizability) of the neighbouring functional group.

Estimating Frequencies of Minority Nevirapine-Resistant Strains in Chronically HIV-1-Infected Individuals Naive to Nevirapine by Using Stochastic Simulations and a Mathematical Model

Nevirapine forms the mainstay of our efforts to curtail the pediatric AIDS epidemic through prevention of mother-to-child transmission of HIV-1. A key limitation, however, is the rapid selection of HIV-1 strains resistant to nevirapine following the administration of a single dose. This rapid selection of resistance suggests that nevirapine-resistant strains preexist in HIV-1 patients and may adversely affect outcomes of treatment. The frequencies of nevirapine-resistant strains in vivo, however, remain poorly estimated, possibly because they exist as a minority below current assay detection limits. Here, we employ stochastic simulations and a mathematical model to estimate the frequencies of strains carrying different combinations of the common nevirapine resistance mutations K103N, V106A, Y181C, Y188C, and G190A in chronically infected HIV-1 patients naive to nevirapine. We estimate the relative fitness of mutant strains from an independent analysis of previous competitive growth assays. We predict that single mutants are likely to preexist in patients at frequencies (similar to 0.01% to 0.001%) near or below current assay detection limits (>0.01%), emphasizing the need for more-sensitive assays. The existence of double mutants is subject to large stochastic variations. Triple and higher mutants are predicted not to exist. Our estimates are robust to variations in the recombination rate, cellular superinfection frequency, and the effective population size. Thus, with 10(7) to 10(8) infected cells in HIV-1 patients, even when undetected, nevirapine-resistant genomes may exist in substantial numbers and compromise efforts to prevent mother-to-child transmission of HIV-1, accelerate the failure of subsequent antiretroviral treatments, and facilitate the transmission of drug resistance.

Valkolakki vai haalarit, vaiko molemmat : Koulutuspolitiikan vaikuttajien näkemykset toisen asteen kehityksestä

In the present research Finnish education policy-makers describe the transformation in upper secondary education in the 1990s. They answered questions related to equality and all-round education. The timeline of the research extends from the early development of the welfare state and equality policy to the 2000s. Its focus is on upper secondary education, which, in this paper, denotes general upper secondary education and vocational upper secondary education. The chronological analysis proceeds from the education committee of 1971 up to the youth education experiment of the 1990s. The voices of the then policy-makers are heard in this research. They were the ones who planned the reforms and/or made the decisions. This being the case, the interviewees include cabinet ministers, permanent secretaries, representatives of organisations and the research community as well as civil servants. The research material can be construed as contextual interpretations of the past, influenced by both the times and places where the narrations were given. The persons interviewed described their experiences and views on education policy. In their narratives they illustrated the transformation that occurred in relation to equality and all-round education. The narrative interviews painted a picture of the upper secondary education transformation and the matriculation examination as having a slowing effect on education policy reforms. It was not until the 1990s when the said examination began to make a difference to students in vocational upper secondary education Those interviewed named the persons who, in their opinion, had the most say in Finnish education policy. This list comprised a small circle of people who more or less agreed on the grand values of education policy, i.e. all-round education and equality. Only a small minority represented a radical view of equality, being true believers in universal upper secondary education implemented in accordance with comprehensive school reform. Finnish education policy was led from the perspective of traditional conception of equality from the 1970s to the 1980s. The transformation finally occurred in the 1990s when equality was understood to mean individual needs and the right to choose. As was the case with matriculation education, the insistence on all-round education also hampered the development of universal upper secondary education. The interviews revealed that any attempts to increase the academic syllabus of vocational education caused organisations as well as other policy-makers to oppose such development well into the 1980s. It was not until the youth education experiment of the 1990s that vocational education finally carved a path to higher education, when the polytechnic schools were made permanent. Three principal groups of key players emerged in the research: ministers of education, civil servants and organisations. The research showed that the ministers and civil servant education policy-makers of the 1990s also included only handful women. The circle of policy-makers was small and represented similar schools of thought. In the 1970s era of government committees, representatives of organisations actively participated in education policy. When the committee establishment was discontinued, this eliminated lobbying venues for the organisations. Nonetheless, the organisations regained their policymaking status in the 1990s. New lobbying organisations included the Finnish Entrepreneurs and the Union of Finnish Upper Secondary School Students. However, in contrast to the 1970s, only rarely would individuals rise from the ranks of organisations to the cadre of policy-makers. The interviewees had a twofold view of neo-liberalism Contrary to other policy-makers, representatives of the research community and organisations concur that neo-liberalism did exist in education policy decision-making in the 1990s.

Segal-Bargmann Transform and Paley-Wiener Theorems on Motion Groups

We study the Segal-Bargmann transform on a motion group R-n v K, where K is a compact subgroup of SO(n) A characterization of the Poisson integrals associated to the Laplacian on R-n x K is given We also establish a Paley-Wiener type theorem using complexified representations

Geometric Characterizations for Patterson-Sullivan Measures of Geometrically Finite Kleinian Groups

The main results of this thesis show that a Patterson-Sullivan measure of a non-elementary geometrically finite Kleinian group can always be characterized using geometric covering and packing constructions. This means that if the standard covering and packing constructions are modified in a suitable way, one can use either one of them to construct a geometric measure which is identical to the Patterson-Sullivan measure. The main results generalize and modify results of D. Sullivan which show that one can sometimes use the standard covering construction to construct a suitable geometric measure and sometimes the standard packing construction. Sullivan has shown also that neither or both of the standard constructions can be used to construct the geometric measure in some situations. The main modifications of the standard constructions are based on certain geometric properties of limit sets of Kleinian groups studied first by P. Tukia. These geometric properties describe how closely the limit set of a given Kleinian group resembles euclidean planes or spheres of varying dimension on small scales. The main idea is to express these geometric properties in a quantitative form which can be incorporated into the gauge functions used in the modified covering and packing constructions. Certain estimation results for general conformal measures of Kleinian groups play a crucial role in the proofs of the main results. These estimation results are generalizations and modifications of similar results considered, among others, by B. Stratmann, D. Sullivan, P. Tukia and S. Velani. The modified constructions are in general defined without reference to Kleinian groups, so they or their variants may prove useful in some other contexts in addition to that of Kleinian groups.

Lacunary Fourier series and a qualitative uncertainty principle for compact Lie groups

We define lacunary Fourier series on a compact connected semisimple Lie group G. If f is an element of L-1 (G) has lacunary Fourier series and f vanishes on a non empty open subset of G, then we prove that f vanishes identically. This result can be viewed as a qualitative uncertainty principle.

Thiol-ene Clickable Hyperscaffolds Bearing Peripheral Allyl Groups

Radical catalyzed thiol-ene reaction has become a useful alternative to the Huisgen-type click reaction as it helps to expand the variability in reaction conditions as well as the range of clickable entities. Thus, direct generation of hyper-branched polymers bearing peripheral allyl groups that could be clicked using a variety of functional thiols would be of immense value. A specifically designed AB(2) type monomer, that carries two allyl benzyl ethers groups and one alcohol functionality, was shown to undergo self-condensation under acid-catalyzed melt-transetherification to yield a hyperbranched polyether that carries numerous allyl end-groups. Importantly, it was shown that the kinetics of polymerization is not dramatically affected by the change of the ether unit from previously studied methyl benzyl ether to an allyl benzyl ether. The peripheral allyl groups were readily clicked quantitatively, using a variety of thiols, to generate an hydrocarbon-soluble octadecyl-derivative, amphiphilic systems using 2-mercaptoethanol and chiral amino acid (N-benzoyl cystine) derivatized hyperbranched structures; thus demonstrating the versatility of this novel class of clickable hyperscaffolds. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49:1735-1744, 2011

Social selection and the evolution of cooperative groups: The example of the cellular slime moulds

In social selection the phenotype of an individual depends on its own genotype as well as on the phenotypes, and so genotypes, of other individuals. This makes it impossible to associate an invariant phenotype with a genotype: the social context is crucial. Descriptions of metazoan development, which often is viewed as the acme of cooperative social behaviour, ignore or downplay this fact. The implicit justification for doing so is based on a group-selectionist point of view. Namely, embryos are clones, therefore all cells have the same evolutionary interest, and the visible differences between cells result from a common strategy. The reasoning is flawed, because phenotypic heterogeneity within groups can result from contingent choices made by cells from a flexible repertoire as in multicellular development. What makes that possible is phenotypic plasticity, namely the ability of a genotype to exhibit different phenotypes. However, co-operative social behaviour with division of labour requires that different phenotypes interact appropriately, not that they belong to the same genotype, or have overlapping genetic interests. We sketch a possible route to the evolution of social groups that involves many steps: (a) individuals that happen to be in spatial proximity benefit simply by virtue of their number; (b) traits that are already present act as preadaptations and improve the efficiency of the group; and (c) new adaptations evolve under selection in the social context-that is, via interactions between individuals-and further strengthen group behaviour. The Dictyostelid or cellular slime mould amoebae (CSMs) become multicellular in an unusual way, by the aggregation of free-living cells. In nature the resulting group can be genetically homogeneous (clonal) or heterogeneous (polyclonal); in either case its development, which displays strong cooperation between cells (to the extent of so-called altruism) is not affected. This makes the CSMs exemplars for the study of social behaviour.

Reaction of diisopropoxytitanium(III) tetrahydroborate with selected organic compounds containing representative functional groups

Diisopropoxytitanium(III) tetrahydroborate, ((PrO)-Pr-1)(2)TiBH4), generated in situ in dichloromethane from diisopropoxytitanium dichloride and benzyltriethylammonium borohydride in a 1:2 ratio selectively reduces aldehydes, ketones, acid chlorides, carboxylic acids, and N-Boc-protected amino acids to the corresponding alcohols in excellent yield under very mild reaction conditions (-78 to 25 degrees C).

Micellar structures of dimeric surfactants with phosphate head groups and wettable spacers: A small-angle neutron scattering study

Dimeric or gemini surfactants consist of two hydrophobic chains and two hydrophilic head groups covalently connected by a hydrophobic or hydrophilic spacer. This paper reports the small-angle neutron scattering (SANS) measurements from aqueous micellar solutions of two different recently developed types of dimeric surfactants: (i) bis-anionic C16H33PO4--(CH2)(m)-PO4-C16H33,2Na(+) dimeric surfactants composed of phosphate head groups and a hydrophobic polymethylene spacer, referred to as 16-m-16,2Na(+), for spacer lengths m = 2, 4, 6, and 10, (ii) bis-cationic C16H33N+(CH3)(2)-CH2-(CH2-O-CH2)(p)-CH2-N+ (CH3)(2)C16H33,2Br(-) dimeric surfactants composed of dimethylammonium head groups and a wettable polyethylene oxide spacer, referred to as 16-CH2-p-CH2-16,2Br(-), for spacer lengths p = 1 - 3. The micellar structures of these surfactants are compared with the earlier studied bis-cationic C16H33N+ (CH3)(2)-(CH2)(m)-N+ (CH3)(2)C16H33,2Br(-) dimeric surfactants composed of dimethylammonium head groups and a hydrophobic polymethylene spacer, referred to as 16-m-16,2Br(-). It is found that 16-m-16,2Na(+), similar to 16-m-16,2Br(-), form various micellar structures depending on the spacer length. Micelles an disklike for rn = 2, rodlike for m = 4, and prolate ellipsoidal fur m = 6 and 10. The micelles of 16-CH2-p-CH2-16,2Br(-) are prolate ellipsoidal for all the values of p = 1 - 3. It is also found that micelles of 16-m-16,2Na(+) and 16-CH2-p-CH2-16,2Br(-) are large in comparison to those of 16-in-16,2Br(-) for similar spacer lengths. This is connected with the fact that both in 16-m-16,2Na(+) and 16-CH2-p-CH2-16,2Br(-), the head group or the spacer is more hydrated as compared to that in the 16-m-16,2Br(-). An increase in the hydration of the spacer or the head group increases the screening of the Coulomb repulsion between the charged head groups. This effect has been found to be more pronounced in the dimeric surfactants having wettable spacers. [S1063-651X(99)00303-7].

Nanotubes of the disulfides of groups 4 and 5 metals

The layered chalcogenides, having structures analogous to graphite, are known to be unstable toward bending and show high propensity to form curved structures, thus eliminating dangling bonds at the edges. Since the discovery of fullerene and nanotube structures of WS2 and MoS2 by Tenne et al. [1-3], there have been attempts to prepare and characterize nanotubes of other layered dichalcogenides with structures analogous to MoS2. Nanotubes of MoS2 and WS2 were prepared by Tenne et al. by reducing the corresponding oxides to the suboxides followed by heating in an atmosphere of forming gas (5 % H-2 + 95 % N-2) and H2S at 700-900 degreesC [1-3]. Alternative methods of synthesis of MoS2 and WS2 nanotubes have since been proposed by employing the decomposition of the ammonium thiometallates or the corresponding trisulfide precursors. This alternative procedure was based on the observation that the trisulfide seems to be formed as an intermediate in the synthesis of the MoS2 and WS2 nanotubes [4]. Accordingly, the decomposition of the trisulfides of MoS2 and W in a reducing atmosphere directly yielded nanotubes of the disulfides MoS2 and WS2 [5]. In this article, we describe the synthesis, structure, and characterization of a few novel nanotubes of the disulfides of groups 4 and 5 metals. These include nanotubes of NbS2, TaS2, ZrS2, and HfS2. The study enlarges the scope of the inorganic nanotubes significantly and promises other interesting possibilities, including the synthesis of the diselenide nanotubes of these metals.

Variants of Miyachi�s Theorem for Nilpotent lie Groups

We formulate and prove two versions of Miyachi�s theorem for connected, simply connected nilpotent Lie groups. This allows us to prove the sharpness of the constant 1/4 in the theorems of Hardy and of Cowling and Price for any nilpotent Lie group. These theorems are proved using a variant of Miyachi�s theorem for the group Fourier transform.