Lions-type compactness and Rubik actions on the Heisenberg group

In this paper we prove a Lions-type compactness embedding result for symmetric unbounded domains of the Heisenberg group. The natural group action on the Heisenberg group TeX is provided by the unitary group U(n) × {1} and its appropriate subgroups, which will be used to construct subspaces with specific symmetry and compactness properties in the Folland-Stein’s horizontal Sobolev space TeX. As an application, we study the multiplicity of solutions for a singular subelliptic problem by exploiting a technique of solving the Rubik-cube applied to subgroups of U(n) × {1}. In our approach we employ concentration compactness, group-theoretical arguments, and variational methods.

Theoretical study on the molecular and electronic properties of some substances used for diabetes mellitus treatment

Diabetes mellitus (DM) is a disease that affects a large number of people, and the number of problems associated with the disease has been increasing in the past few decades. These problems include cardiovascular disorders, blindness and the eventual need to amputate limbs. Therefore, the quality of life for people living with DM is less than it is for healthy people. In several cases, metabolic syndrome (MS), which can be considered a disturbance of the lipid metabolism, is associated with DM. In this work, two drugs used to treat DM, pioglitazone and rosiglitazone, were studied using theoretical methods, and their molecular properties were related to the biological activity of these drugs. From the results, it was possible to correlate the properties of each substance-particularly electronic properties-with the biological interactions that are linked to their pharmacological effects. These results suggest that there are future prospects for designing or developing new drugs based on the correlation between theoretical and experimental properties.

Engendering Group Support Based Foresight for Capital Intensive Manufacturing Industries - Case Paper and Steel Industry Scenarios by 2018

In recent times of global turmoil, the need for uncertainty management has become ever momentous. The need for enhanced foresight especially concerns capital-intensive industries, which need to commit their resources and assets with long-term planning horizons. Scenario planning has been acknowledged to have many virtues - and limitations - concerning the mapping of the future and illustrating the alternative development paths. The present study has been initiated to address both the need of improved foresight in two capital-intensive industries, i.e. the paper and steel industries and the imperfections in the current scenario practice. The research problem has been approached by engendering a problem-solving vehicle, which combines, e.g. elements of generic scenario process, face-to-face group support methods, deductive scenario reasoning and causal mapping into a fully integrated scenario process. The process, called the SAGES scenario framework, has been empirically tested by creating alternative futures for two capital-intensive industries, i.e. the paper and steel industries. Three scenarios for each industry have been engendered together with the identification of the key megatrends, the most important foreign investment determinants, key future drivers and leading indicators for the materialisation of the scenarios. The empirical results revealed a two-fold outlook for the paper industry, while the steel industry future was seen as much more positive. The research found support for utilising group support systems in scenario and strategic planning context with some limitations. Key perceived benefits include high time-efficiency, productivity and lower resource-intensiveness. Group support also seems to enhance participant satisfaction, encourage innovative thinking and provide the users with personalised qualitative scenarios.

Electrochemical and theoretical evaluation of the interaction between dna and amodiaquine: evidence of the guanine adduct formation

The electrochemical behavior of the interaction of amodiaquine with DNA on a carbon paste electrode was studied using voltametric techniques. In an acid medium, an electroactive adduct is formed when amodiaquine interacts with DNA. The anodic peak is dependent on pH, scan rate and the concentration of the pharmaceutical. Adduct formation is irreversible in nature, and preferentially occurs by interaction of the amodiaquine with the guanine group. Theoretical calculations for optimization of geometry, and DFT analyses and on the electrostatic potential map (EPM), were used in the investigation of adduct formation between amodiaquine and DNA.

Innovaatio-ohjelmatoiminnan suorituskyvyn mittaus

Tutkimuksen tavoitteena on luoda viitekehys yritysten innovaatiotoimintaa ohjelmatoiminnalla tukevan julkisen organisaation suorituskyvyn mittaamiseksi. Tutkimus on luonteeltaan tapaustutkimus ja tutkimusotteena siinä käytetään toiminta-analyyttistä tutkimusotetta. Tutkimuksen empiirinen aineisto kerättiin havainnoimalla, keskusteluilla, haastatteluilla sekä ryhmätyöskentely-menetelmillä. Luodun viitekehyksen mukaan innovaatiotoimintaa ohjelmatoiminnalla tukevan julkisen organisaation tuottama julkinen arvo syntyy pienentämällä innovaatio-toiminnan markkina- ja järjestelmähäiriöitä, joka tapahtuu tarjoamalla rahalista tukea sekä palveluita. Näin innovaatiotoiminnan tuloksellisuus ja positiiviset ulkoisvaikutukset lisääntyvät. Tämä johtaa lopulta talouden kasvamiseen sekä yhteiskunnan ja ympäristön hyvinvointiin. Innovaatiotuella voidaan säädellä myös innovaatiotoiminnan aluetta ja näin luoda arvoa pureutumalla yhteiskunnan ongelmakohtiin. Tämän lisäksi kansalaisille on todennäköisesti arvokasta organisaatiota kohtaan tuntema luottamus, jota kasvattavat luultavasti esimerkiksi resurssien tehokas käyttö, oikeudenmukainen toiminta, asiakkaiden yhden-mukainen kohtelu, todennetut tulokset ja vaikutukset sekä toiminnan läpinäkyvyys. Viitekehyksen pohjalta muodostettiin Ohjelmat-ydinprosessin suorituskyvyn mittaristo. Aluksi kuvattiin ydinprosessin tavoitteet, joita tarkennettiin vaikuttavuusmallilla sekä sidosryhmäanalyysillä. Seuraavaksi muodostettiin ydinprosessille strategiakartta ja tunnistettiin sen kriittiset menestystekijät. Tuloksena syntyi mittaristo, jossa on 84 potentiaalista prosessin suorituskykyä mittaavaa mittaria. Lopuksi mittaristoa tarkasteltiin kokonaisuutena ja todettiin se kohtalaisen hyvin onnistuneeksi.

On the Nucleophilicity of Boryllithium Compounds. A Theoretical Study

Boron compounds are widely used in synthetic chemistry. The synthesis of the compounds is relatively easy, presenting thermodynamic stability and synthetic versatility. Almost all of them show electrophilic reactivity. Recently, some boryllithium species have been reported as a base or a nucleophile in reaction with organic electrophiles in S(N)2 reactions. In the present work, the proton affinity (PA) of boryllithium compounds was calculated. These values can be useful as theoretical reference values and to provide valuable complementary information for the interpretation and discussion of the basicity of these compounds. The proton affinity was calculated using a theoretical method based on density functional theory and high-level theoretical methods through MP2 and G2MP2 levels of theory. In addition, some global and local reactivity indexes based on density functional theory (DFT) on boryllithium compounds were studied. In order to compare and discuss the chemical reactivity of these compounds, some analogues and electrophilic boron compounds were also studied. Our results showed a local and global nucleophilic reactivity of the boryllithium molecules in agreement with the experimental. reactivity. The boryllithium compounds revealed to be strong bases in comparison to other analogue compounds studied in this work.

The effect of carbonyl group in the asymmetry Of (3,4)J(CH) coupling constants in norbornanones

A rationalization of the known difference between the (3,4)J(C4H1) and (3,4)J(C1H4) couplings transmitted mainly through the 7-bridge in norbornanone is presented in terms of the effects of hyperconjugative interactions involving the carbonyl group. Theoretical and experimental studies Of (3,4)J(CH) couplings were carried out in 3-endo- and 3-exo-X-2-norbornanone derivatives (X = Cl, Br) and in exo- and endo-2-noborneol compounds. Hyperconjugative interactions were studied with the natural bond orbital (NBO) method. Hyperconjugative interactions involving the carbonyl pi*c(2) =o and sigma*c(2) =o antibonding orbitals produce a decrease of three-bond contribution to both (3,4) J(C4H1) and (3,4)J(C1H4) couplings. However, the latter antibonding orbital also undergoes a strong sigma c(3)-c(4) ->sigma*c(2) =o interaction, which defines an additional coupling pathway for (3,4)J(C4H1) but not for (3,4)J(C1H4). This pathway is similar to that known for homoallylic couplings, the only difference being the nature of the intermediate antibonding orbital; i.e. for (3,4)J(C4H1) it is of sigma*-type, while in homoallylic couplings it is of pi*-type. Copyright (c) 2007 John Wiley & Sons, Ltd.

Strategies for the use of PIMEX and other video exposure monitoring methods. : Final report from sub-project “implementation strategies” within the HERIVIS project

Video exposure monitoring (VEM) is a group of methods used for occupational hygiene studies. The method is based on a combined use of video recordings with measurements taken with real-time monitoring instruments. A commonly used name for VEM is PIMEX. Since PIMEX initially was invented in the mid 1980’s have the method been implemented and developed in a number of countries. With the aim to give an updated picture of how VEM methods are used and to investigate needs for further development have a number of workshops been organised in Finland, UK, the Netherlands, Germany and Austria. Field studies have also been made with the aim to study to what extent the PIMEX method can improve workers motivation to actively take part in actions aimed at workplace improvements.The results from the workshops illustrates clearly that there is an impressive amount of experiences and ideas for the use of VEM within the network of the groups participating in the workshops. The sharing of these experiences between the groups, as well as dissemination of it to wider groups is, however, limited. The field studies made together with a number of welders indicate that their motivation to take part in workplace improvements is improved after the PIMEX intervention. The results are however not totally conclusive and further studies focusing on motivation are called for.It is recommended that strategies for VEM, for interventions in single workplaces, as well as for exposure categorisation and production of training material are further developed. It is also recommended to conduct a research project with the intention of evaluating the effects of the use of VEM as well as to disseminate knowledge about the potential of VEM to occupational hygiene experts and others who may benefit from its use.

Electrochemical and theoretical evaluation of the interaction between dna and amodiaquine: evidence of the guanine adduct formation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Discrete generator coordinate: Symmetry restoration in finite-dimensional spaces

Group theoretical-based techniques and fundamental results from number theory are used in order to allow for the construction of exact projectors in finite-dimensional spaces. These operators are shown to make use only of discrete variables, which play the role of discrete generator coordinates, and their application in the number symmetry restoration is carried out in a nuclear BCS wave function which explicitly violates that symmetry. © 1999 Published by Elsevier Science B.V. All rights reserved.

Theoretical investigation of the interaction of a polymer film with a nanoparticle

The fundamental aim in our investigation of the interaction of a polymer film with a nanoparticle is the extraction of information on the dynamics of the liquid using a single tracking particle. In this work two theoretical methods were used: one passive, where the motion of the particle measures the dynamics of the liquid, one active, where perturbations in the system are introduced through the particle. In the first part of this investigation a thin polymeric film on a substrate is studied using molecular dynamics simulations. The polymer is modeled via a 'bead spring' model. The particle is spheric and non structured and is able to interact with the monomers via a Lennard Jones potential. The system is micro-canonical and simulations were performed for average temperatures between the glass transition temperature of the film and its dewetting temperature. It is shown that the stability of the nanoparticle on the polymer film in the absence of gravity depends strongly on the form of the chosen interaction potential between nanoparticle and polymer. The relative position of the tracking particle to the liquid vapor interface of the polymer film shows the glass transition of the latter. The velocity correlation function and the mean square displacement of the particle has shown that it is caged when the temperature is close to the glass transition temperature. The analysis of the dynamics at long times shows the coupling of the nanoparticle to the center of mass of the polymer chains. The use of the Stokes-Einstein formula, which relates the diffusion coefficient to the viscosity, permits to use the nanoparticle as a probe for the determination of the bulk viscosity of the melt, the so called 'microrheology'. It is shown that for low frequencies the result obtained using microrheology coincides with the results of the Rouse model applied to the polymer dynamics. In the second part of this investigation the equations of Linear Hydrodynamics are solved for a nanoparticle oscillating above the film. It is shown that compressible liquids have mechanical response to external perturbations induced with the nanoparticle. These solutions show strong velocity and pressure profiles of the liquid near the interface, as well as a mechanical response of the liquid-vapor interface. The results obtained with this calculations can be employed for the interpretation of experimental results of non contact AFM microscopy

A molecular phylogeny of bivalve mollusks: ancient radiations and divergences as revealed by mitochondrial genes

The main scope of my PhD is the reconstruction of the large-scale bivalve phylogeny on the basis of four mitochondrial genes, with samples taken from all major groups of the class. To my knowledge, it is the first attempt of such a breadth in Bivalvia. I decided to focus on both ribosomal and protein coding DNA sequences (two ribosomal encoding genes -12s and 16s -, and two protein coding ones - cytochrome c oxidase I and cytochrome b), since either bibliography and my preliminary results confirmed the importance of combined gene signals in improving evolutionary pathways of the group. Moreover, I wanted to propose a methodological pipeline that proved to be useful to obtain robust results in bivalves phylogeny. Actually, best-performing taxon sampling and alignment strategies were tested, and several data partitioning and molecular evolution models were analyzed, thus demonstrating the importance of molding and implementing non-trivial evolutionary models. In the line of a more rigorous approach to data analysis, I also proposed a new method to assess taxon sampling, by developing Clarke and Warwick statistics: taxon sampling is a major concern in phylogenetic studies, and incomplete, biased, or improper taxon assemblies can lead to misleading results in reconstructing evolutionary trees. Theoretical methods are already available to optimize taxon choice in phylogenetic analyses, but most involve some knowledge about genetic relationships of the group of interest, or even a well-established phylogeny itself; these data are not always available in general phylogenetic applications. The method I proposed measures the "phylogenetic representativeness" of a given sample or set of samples and it is based entirely on the pre-existing available taxonomy of the ingroup, which is commonly known to investigators. Moreover, it also accounts for instability and discordance in taxonomies. A Python-based script suite, called PhyRe, has been developed to implement all analyses.

Solid-state NMR on columnar supramolecular structures

The present work deals with the characterisation of three columnar self-assembled systems, that is, benzene-1,3,5-tricarboxamides, a peripherally thioalkyl-substituted phthalocyanine, and several oligo-(p-phenylenevinylene)s. In order to probe the supramolecular organisation solid-state NMR has been used as the main technique, supported by X-ray measurements, theoretical methods, and thermal analysis. rnrnBenzene-1,3,5-tricarboxamides (BTAs) turned out to be well suited model compounds to study various fundamental supramolecular interactions, such as π-π-interactions, hydrogen bonding, as well as dynamic and steric effects of attached side chains. Six BTAs have been investigated in total, five with a CO-centred amide group bearing different side chains and one with an inverted N-centred amide group. The physical properties of these BTAs have been investigated as a function of temperature. The results indicated that in case of the CO-centred BTAs the stability of the columnar mesophase depends strongly on the nature of the side chains. Further experiments revealed a coplanar orientation of adjacent BTA molecules in the columnar assembly of CO-centred BTAs, whereas the N-centred BTA, showed a deviating not fully coplanar arrangement. These differences were ascribed to distinct hydrogen bonding schemes, involving a parallel alignment of hydrogen bonds in case of CO-centred BTAs and an antiparallel alignment in case of the N-centred counterpart.rnrn The fundamental insights of the supramolecular organisation of BTAs could be partially adapted to an octa-substituted phthalocyanine with thiododecyl moieties. Solid-state NMR in combination with chemical shift calculations determined a tilted herringbone arrangement of phthalocyanine rings in the crystalline phase as well as in the mesophase. Moreover, 1H NMR measurements in the mesophase of this compound suggested an axial rotation of molecules, which is inhibited in the crystalline phase.rnrnAs a third task, the supramolecular assembly of oligo-(p-phenylenevinylene)s of varying length and with different polar head groups have been investigated by a combined X-ray and solid-state NMR study. The results revealed a columnar structure formation of these compounds, being promoted by phase separation of alkyl side chains and aromatic rigid rods. In this system solid-state NMR yielded meaningful insight into the isotropisation process of butoxy and 2-S-methylbutoxy substituted oligo-(p-phenylenevinylene) rods.rn

Canonical group quantization and boundary conditions

In the present thesis, we study quantization of classical systems with non-trivial phase spaces using the group-theoretical quantization technique proposed by Isham. Our main goal is a better understanding of global and topological aspects of quantum theory. In practice, the group-theoretical approach enables direct quantization of systems subject to constraints and boundary conditions in a natural and physically transparent manner -- cases for which the canonical quantization method of Dirac fails. First, we provide a clarification of the quantization formalism. In contrast to prior treatments, we introduce a sharp distinction between the two group structures that are involved and explain their physical meaning. The benefit is a consistent and conceptually much clearer construction of the Canonical Group. In particular, we shed light upon the 'pathological' case for which the Canonical Group must be defined via a central Lie algebra extension and emphasise the role of the central extension in general. In addition, we study direct quantization of a particle restricted to a half-line with 'hard wall' boundary condition. Despite the apparent simplicity of this example, we show that a naive quantization attempt based on the cotangent bundle over the half-line as classical phase space leads to an incomplete quantum theory; the reflection which is a characteristic aspect of the 'hard wall' is not reproduced. Instead, we propose a different phase space that realises the necessary boundary condition as a topological feature and demonstrate that quantization yields a suitable quantum theory for the half-line model. The insights gained in the present special case improve our understanding of the relation between classical and quantum theory and illustrate how contact interactions may be incorporated.

Theoretical Calculations of Acid Dissociation Constants: A Review Article

Acid dissociation constants, or pKa values, are essential for understanding many fundamental reactions in chemistry. These values reveal the deprotonation state of a molecule in a particular solvent. There is great interest in using theoretical methods to calculate the pKa values for many different types of molecules. These include molecules that have not been synthesized, those for which experimental pKa determinations are difficult, and for larger molecules where the local environment changes the usual pKa values, such as for certain amino acids that are part of a larger polypeptide chain. Chemical accuracy in pKa calculations is difficult to achieve, because an error of 1.36 kcal/mol in the change of free energy for deprotonation in solvent results in an error of 1 pKa unit. In this review the most valuable methods for determining accurate pKa values in aqueous solution are presented for educators interested in explaining or using these methods for their students.