Experimental and theoretical investigation of molecular structure and conformation of the 4-isopropylthioxanthone

In this study, the molecular structure and conformational analyses of the 4-isopropylthioxanthone (4-ITX) are reported according to experimental and theoretical results. The compound crystallizes in the centrosymmetric P (1) over bar space group with only one molecule in the asymmetric unit, presenting the most stable conformation, in which the three fused-rings adopt a planar geometry, and the isopropyl group assumes a torsional angle with less sterical hindrance. The structural and conformational analyses were performed using theoretical calculations such as Hartree-Fock (HF), DFT method in combination with 6-311G(d,p) and 6-31++G(d,p) and the results were compared with infrared spectroscopy (FT-IR) and X-ray diffraction (XRD). The supramolecular assembly of 4-ITX is kept by non-classical C-H center dot center dot center dot O hydrogen bonds and weak interactions such as pi-pi stacking. 4-ITX was also studied by (1)H and (13)C NMR spectroscopy. UV-Vis absorption spectroscopic properties of the 4-ITX showed the long-wavelength maximum shifts towards high energy when the solvent polarity increases. (C) 2011 Elsevier B.V. All rights reserved.

Designing Novel Antitrypanosomal Agents from a Mixed Graph-Theoretical Substructural Approach

Chagas disease is nowadays the most serious parasitic health problem. This disease is caused by Trypanosoma cruzi. The great number of deaths and the insufficient effectiveness of drugs against this parasite have alarmed the scientific community worldwide. In an attempt to overcome this problem, a model for the design and prediction of new antitrypanosomal agents was obtained. This used a mixed approach, containing simple descriptors based on fragments and topological substructural molecular design descriptors. A data set was made up of 188 compounds, 99 of them characterized an antitrypanosomal activity and 88 compounds that belong to other pharmaceutical categories. The model showed sensitivity, specificity and accuracy values above 85%. Quantitative fragmental contributions were also calculated. Then, and to confirm the quality of the model, 15 structures of molecules tested as antitrypanosomal compounds (that we did not include in this study) were predicted, taking into account the information on the abovementioned calculated fragmental contributions. The model showed an accuracy of 100% which means that the ""in silico"" methodology developed by our team is promising for the rational design of new antitrypanosomal drugs. (C) 2009 Wiley Periodicals, Inc. J Comput Chem 31: 882-894. 2010

Photoluminescence study of new lanthanide complexes with benzeneseleninic acids

New lanthanide complexes with benzeneseleninic (ABSe) and 4-chloro-benzeneseleninic (ABSeCl) acids have been synthesized and characterized by elemental analysis, infrared and UV-visible spectroscopies. The emission spectra of the trivalent europium complexes presented the typical electronic (5)D(0) -> (7)F(j) transitions of the ion (J = 0-4). The ground-state geometries of the europium complexes have been calculated by using the Sparkle/AM1 model. From these results, the 4f-4f intensity parameters and energies of the ligand singlet and triplet excited states have been obtained. The lower emission quantum yield for the [Eu(ABSe)(3)(H(2)O)(2)](H(2)O)(2) compound, as compared to the [Eu(Al(3)SeCl)(3)(H(2)O)(2)] one, can be associated to the higher numbers of water molecules, in the first and second coordination spheres, that contribute to the luminescence quenching. The [Eu(Al(3)Se)(3)(H(2)O)(2)](H(2)O)(2) complex presents an intermediate state whose energy difference with respect to the first excited singlet state is resonant with three phonons from the water molecules, favouring a multiphonon relaxation process from the singlet state followed by a fast internal conversion process; this effect is less pronounced in the complex with the ABSeCl ligand. The luminescence decay curves of the gadolinium complexes indicate that the level responsible for the intramolecular energy transfer process has a triplet character for both compounds. The nephelauxetic effect in these compounds was investigated under the light of a recently proposed covalency scale based on the concept of overlap polarizability of the chemical bond. (C) 2009 Elsevier B.V. All rights reserved.

Structural and spectroscopic properties of the diazocarbene radical (CNN) and its ions CNN(+) and CNN(-): a high-level theoretical investigation

The diazocarbene radical, CNN, and the ions CNN(+) and CNN(-) were investigated at a high level of theory. Very accurate structural parameters for the states X(3)Sigma(-) and A(3)Pi of CNN, and X(2)Pi of both CNN(+) and CNN(-) were obtained with the UCCSD(T) method using correlated-consistent basis functions with extrapolations to the complete basis set limit, with valence only and also with all electrons correlated. Harmonic and anharmonic frequencies were obtained for all species and the Renner parameter and average frequencies evaluated for the Pi states. At the UCCSD(T)/CBS(T-5) level of theory, Delta(f)H(0 K) = 138.89 kcal/mol and Delta(f)H(298 K) = 139.65 kcal/mol were obtained for diazocarbene; for the ionization potential and the electron affinity of CNN, 10.969 eV (252.95 kcal/mol), and 1.743 eV (40.19 kcal/mol), respectively, are predicted. Geometry optimization was also carried out with the CASSCF/MRCI/CBS(T-5) approach for the states X(3)Sigma(-) A(3)Pi, and a(1)Delta of CNN, and with the CASSCF/MRSDCI/aug-cc-pVTZ approach for the states b(1)Sigma(+), c(1)Pi, d(1)Sigma(-), and B(3)Sigma(-), and excitation energies (T(e)) evaluated. Vertical energies were calculated for 15 electronic states, thus improving on the accuracy of the five transitions already described, and allowing for a reliable overview of a manifold of other states, which is expected to guide future spectroscopic experiments. This study corroborates the experimental assignment for the vertical transition X (3)Sigma(-) <- E (3)Pi.

Design of novel antituberculosis compounds using graph-theoretical and substructural approaches

The increasing resistance of Mycobacterium tuberculosis to the existing drugs has alarmed the worldwide scientific community. In an attempt to overcome this problem, two models for the design and prediction of new antituberculosis agents were obtained. The first used a mixed approach, containing descriptors based on fragments and the topological substructural molecular design approach (TOPS-MODE) descriptors. The other model used a combination of two-dimensional (2D) and three-dimensional (3D) descriptors. A data set of 167 compounds with great structural variability, 72 of them antituberculosis agents and 95 compounds belonging to other pharmaceutical categories, was analyzed. The first model showed sensitivity, specificity, and accuracy values above 80% and the second one showed values higher than 75% for these statistical indices. Subsequently, 12 structures of imidazoles not included in this study were designed, taking into account the two models. In both cases accuracy was 100%, showing that the methodology in silico developed by us is promising for the rational design of antituberculosis drugs.

Excited states of the CaAl molecule: An MRCI study

Accurate potential energy curves, dissociation energies and spectroscopic constants for several low-lying doublet and quartet electronic states of CaAl were investigated using the CASSCF/MRCI methodology, and the cc-pVQZ basis set. Our results represent an improvement over a previous theoretical description, and also characterizes new higher excited states not previously investigated, thus confirming the assignment of four excited states investigated experimentally. With the theoretical transition moment functions, transition probabilities and radiative lifetimes were estimated via Einstein spontaneous emission coefficients. (c) 2008 Elsevier B. V. All rights reserved.

First study on the thermo-solvatochromism in aqueous 1-(1-butyl)-3-methylimidazolium tetrafluoroborate: A comparison between the solvation by an ionic liquid and by aqueous alcohols

The thermo-solvatochrornic behaviors of 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl) phenolate, RB; 2,6-dichloro-4-(2,4,6-triphenyloyridinium-1-yl) phenolate, WB; 2,6-dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr(2); 2,6-dibromo-4-[(E)-2-(1-n-octylpyridinium-4-yl)ethenyl] phenolate, OcPMBr(2), have been investigated in binary mixtures of the ionic liquid, IL, 1-(1-butyl)-3-methylimidazolium tetrafluorborate, [BuMeIm][BF(4)], and water (W), in the temperature range from 10 to 60 degrees C. Plots of the empirical solvent polarities, ET (probe) in kcal mol(-1), versus the mole fraction of water in the binary mixture, chi(w) showed nonlinear, i.e., nonideal behavior. Solvation by these IL-W mixtures shows the following similarities to that by aqueous aliphatic alcohols: The same solvation model can be conveniently employed to treat the data obtained; it is based on the presence in the system-bulk medium and probe solvation shell of IL, W, and the ""complex"" solvent 1:1 IL-W. The origin of the nonideal solvation behavior appears to be the same, preferential solvation of the probe, in particular by the complex solvent. The strength of association of the IL-W complex, and the polarity of the IL are situated between the corresponding values of aqueous methanol and aqueous ethanol. Temperature increase causes a gradual desolvation of all probes employed. A difference between solvation by IL-W and aqueous alcohols is that probe-solvent hydrophobic interactions appear to play a minor role in case of the former mixture, probably because solvation is dominated by hydrogen-bonding and Coulombic interactions between the ions of the IL and the zwitterionic probes.

A CASSCF/MRCI Study of the Low-Lying Electronic States of the BeS Molecule

Accurate potential energy curves, dipole moment functions, dissociation energies, and molecular constants for several low-lying singlet and triplet electronic states of BeS were investigated using the CASSCF/MRCI methodology, and the cc-pV5Z basis set for beryllium, and the aug-cc-pV(5+d) Z set for sulfur. Besides presenting improved results for the three lowest lying states, this study presents the first theoretical characterization of another set of nine excited states so far unknown experimentally. Our results are sufficiently accurate to reliably guide the experimental search and characterization of these states, and also to confirm the experimental assignment of the B(1)Sigma(+) excited state. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1694-1700, 2011

The origin of the molecular interaction between amino acids and gold nanoparticles: A theoretical and experimental investigation

This study describes the synthesis of novel biological hybrid materials, where 3D structures were obtained using gold nanoparticles (AuNps) and methionine (Met) in a one-step procedure in aqueous media. The type of nanostructure can be controlled by tuning the intermolecular interactions between Met and AuNp, which strongly depends on the pH used for the synthesis. Computational simulation using the density-functional theory (DFT) showed that the AuNp - Met 3D structures are formed upon reorientation of Met molecules so that the backbone amine groups interact via H-bonds. These findings were experimentally confirmed using FTIR and UV-vis spectroscopy. Crown Copyright (C) 2008 Published by Elsevier B. V. All rights reserved.

A comparative study of immigrants’ political participation in Sweden and the Netherlands

This study deals with immigrants’ political participation in Sweden and the Netherlands. Scholars have recognized low level of political participation of immigrants in Sweden compared to the Netherlands. The main goal of this study is to analyze the institutional influence, mainly from political parties over immigrants’ motivation for active electoral participation. The modified actor-context model uses here as the main theoretical framework. In addition, social capital theory employs to analyze immigrants’ voluntary organizational membership. This study confirms that, Swedish immigrants have the lower participation rate in the political sphere, at lest to a certain extent, than its counterparts the Dutch immigrants. This study also confirms the argument that contextual factors can influence actor’s motivations in integration-oriented action, and similarly it validates the necessity of enlargement of the actor-context model.

Gender Equality a case study of Sweden : Gender Equality Gender Equity and policies of combating inequality at workplace to make the society equal.

The paper analyses Gender Equality, Gender Equity and policies of combating inequality at workplace to make the society equal as a case study of Sweden. The aim of paper is see the gender equality, gender equity, discrimination against women at workplace and to describe the policies combating inequality in the welfare state of Sweden. This work highlights the gender equality in terms of institutionalizing gender equality, gender equity, gender and pay gap, parental leave, gender and the pension system and sexual behavior directed towards women and policies combating inequality to bring equality in society. For my research I used the secondary data the fact sheets, scientific literature, statistics from eurostate of Sweden and case studies about Swedish society and the theoretical explanation to explain the phenomena. To achieve my aim I used the combination of both qualitative and quantitative methods of research. I showed the empirical evidences of these phenomena from the Swedish society and theoretical analysis about equality and equity of gender in different wakes of life. I found an interesting conclusion that there are good policies and legislation to combat inequality to bring society but there are no policies to change the perception of society about male and female role.

Brand Awareness among Customers : A case study of ICA-Kvantum

This research paper has been prepared by Bachelor students from Dalarna University in Borlänge. The project is centered on a case study of ICA – Kvantum and its brand awareness among customers. The purpose of this study is to find out that which measures can help ICA-Kvantum to create brand awareness among its current and potential customers by looking in to the importance of information of its offerings and use of effective communication tools to convey this information. Further, to recommend them what they need to do, to increase brand awareness among their customers with the help of managerial implications. The research question was formulated as what actions could be seen effective for ICA-Kvantum to maintain or improve brand awareness among its current and potential customers.The project was created with the help of theoretical concepts of brand awareness, brand loyalty, perceived quality, consumer decision model, integrated marketing communication approach and strategic planning process. These theories were applied in this thesis in order to find out the most effective communication measures to maintain or improve brand awareness among current and potential customers of ICA-Kvantum.The primary and secondary data was collected. Primary data was gathered through the survey among ICA-Kvantum customers in the front of the store in Borlänge. The personal interview with manager was conducted in the office of ICA-Kvantum store located in Borlänge. Secondary data was gathered from textbooks, academic journals, theses and websites.The empirical findings have been presented in detail and then analyzed with the help of theoretical concepts. The analysis and further results from survey and interview focused on importance of information, marketing communication tools, brand awareness and loyalty, perceived quality and implementation of strategic planning process. Moreover, the main weaknesses and strengths of ICA-Kvantun have been evaluated. The conclusion including short summary of analysis and its results have been provided at the end. Each weakness of issues related to brand awareness i.e. importance of information, effectiveness of marketing communication tools and strengths and weaknesses of ICA-Kvantum discussed in the paper, has been pointed out along with solutions and managerial implications.

Värdigt liv och välbefinnande, enligt vem? : en kvalitativ studie om brukare och biståndshandläggares beskrivningar av ett värdigt liv och välbefinnande : Dignity and well-being, according to whom? : a qualitative study of elderly and assistance officer´s descriptions of a dignified life and wellbeing

We are two students named Susanne Grönlund and Anna Zaar and have jointly worked together this c-essay called "dignity and well-being according to whom? The paper is written at Högskolan dalarna in Falun.The purpose of this study was to investigate how the elderly and assistance officer describes dignity and well-being and how it is consistent with the government's bill on the national values that the National Board has developed.Our empirical study consists of four qualitative interviews, two older people dependent on community care and two assistance officers. The study's theoretical basis is Antonovsky's salutogenic approach and SOC. The survey focuses on different themes such as dignity, integrity, participation, treatment, wellbeing, security and meaningfulness which are also central themes in the Government Bill on the national values for elderly.The results show that the respondents believe that a life of dignity is difficult to define and also a subjective experience. The results also show a consistency between what the elderly, assistance officer and the national values that define dignity and well-being. Social Services Act, national values should serve as a starting point for municipalities to improve elderly care, thereby creating a sense of coherence for the individual. Keywords: Elder care, dignity, integrity, participation, attitude, well-being, security and meaningfulness.

Small-Scale Farmers Land Use and Socioeconomic Situation in the Mount Elgon District in Northwestern Kenya : A Minor Field Study - Combined Field Mapping and Interview

This Minor Field Study was carried out during November and December in 2011 in the Mount Elgon District in Western Kenya. The objective was to examine nine small-scale farming household´s land use and socioeconomic situation when they have joined a non-governmental organization (NGO) project, which specifically targets small-scale farming households to improve land use system and socioeconomic situation by the extension of soil and water conservation measures. The survey has worked along three integral examinations methods which are mapping and processing data using GIS, semi structured interviews and literature studies.   This study has adopted a theoretical approach referred to as political ecology, in which landesque capital is a central concept. The result shows that all farmers, except one, have issues with land degradation. However, the extent of the problem and also implemented sustainable soil and water conservation measures were diverse among the farmers. The main causes of this can both be linked to how the farmers themselves utilized their farmland and how impacts from the climate change have modified the terms of the farmers working conditions. These factors have consequently resulted in impacts on the informants’ socioeconomic conditions. Furthermore it was also registered that social and economic elements, in some cases, were the causes of how the farmers manage their farmland. The farmer who had no significant problem with soil erosion had invested in trees and opportunities to irrigate the farmland. In addition, it was also recorded that certain farmers had invested in particular soil and water conservation measures without any significant result. This was probably due to the time span these land measures cover before they start to generate revenue.  The outcome of this study has traced how global, national and local elements exist in a context when it comes to the conditions of the farmers´ land use and their socioeconomic situation. The farmers atMt.Elgon are thereby a component of a wider context when they are both contributory to their socioeconomic situation, mainly due to their land management, and also exposed to core-periphery relationships on which the farmers themselves have no influence.

Ways of knowing in ways of moving : A study of the meaning of capability to move

The overall aim of this thesis has been to investigate the meaning of the capability to move in order to identify and describe this capability from the perspective of the one who moves in relation to specific movements. It has been my ambition to develop ways to explicate, and thereby open up for discussion, what might form an educational goal in the context of movements and movement activities in the school subject of physical education and health (PEH). In this study I have used a practical epistemological perspective on capability to move, a perspective that challenges the traditional distinction between mental and physical skills as well as between theoretical and practical knowledge. Movement actions, or ways of moving, are seen as expressions of knowing. In order to explore an understanding of the knowing involved in specific ways of moving, observations of  actors’ ways of moving and their own experiences of moving were brought together. Informants from three different arenas took part: from PEH in upper secondary school, from athletics and from free-skiing. The results of the analyses suggest it is possible to describe practitioners’ developed knowing as a number of specific ways of knowing that are in turn related to specific ways of moving. Examples of such specific ways of moving may be discerning and modifying one’s own rotational velocity and navigating one’s (bodily) awareness. Additionally, exploring learners’ pre-knowing of a movement ‘as something’ may be fruitful when planning the teaching and learning of capability to move. I have suggested that these specific ways of knowing might be regarded as educational goals in PEH. In conducting this study, I have also had the ambition to contribute to the ongoing discussion of what ‘ability’ in the PEH context might mean. In considering specific ways of knowing in moving, the implicit and taken-for-granted meaning of ‘standards of excellence’ and ‘sports ability’can be discussed, and challenged.