Spectroscopic and theoretical studies of some N,N-diethyl-2-[(4 `-substituted)phenylsulfonyl]acetamides

The analysis of the IR carbonyl band of the N,N-diethyl-2-[(4`-substituted)phenylsulfonyl]acetamides Et(2)NC(O)CH(2)S(O)(2)-C(6)H(4)-Y (Y = OMe 1, Me 2,1-13, Cl 4, Br 5, NO(2) 6) supported by B3LYP/6-31G(d,p) calculations for 3, indicated the existence of three pairs (anti and syn) of cis (c) and gauche (g(1) and g(2)) conformers in the gas phase, being the gauche conformers significantly more stable than the cis ones. The anti geometry is more stable than the syn one, for each pair of cis and gauche conformers. The summing up of the orbital (NBO analysis) and electrostatic interactions justifies quite well the populations and the v(CO) frequencies of the anti and syn pairs of c, g(1) and g(2) conformers. The IR higher carbonyl frequency component whose population is ca. 10%, in CCl(4), may be ascribed to the least stable and most polar cis conformer pair (in the gas phase) and the lower frequency component whose population is ca. 90%, to the summing up of the populations of the two most stable and least polar gauche conformer pairs (g(1) and g(2)) (in the gas phase). The reversal of the cis(c)/gauche (g(1) + g(2)) population ratio observed in chloroform ca. 60% (cis)/40% (gauche) and the occurrence of the most polar cis(c) conformer only, in acetonitrile, strongly suggests the coalescence of the two gauche components in a unique carbonyl band in solution. A further support to this rationalization is given by the single point PCM solvation model performed by HF/6-31G(d,p) method, which showed a progressive increase of the c/(g(1) + g(2)) ratio going from gas to CCl(4), to CHCl(3) and to CH(3)CN. X-ray single crystal analysis of 4 indicates that this compound assumes, in the solid state, the syn-clinal (gauche) conformation with respect to the [O=C-CH(2)-S] moiety, and the most stable anti geometry relative to the [C(O)N(CH(2)CH(3))(2)] fragment. In order to obtain larger energy gain from the crystal packing the molecules of 4 are linked in centrosymmetric dimers through two C-H center dot center dot center dot O interactions (C-H([O-Ph])center dot center dot center dot O([SO2])) forming a step ladder. (C) 2011 Elsevier B.V. All rights reserved.

Photocatalytic degradation of methylene blue by TiO(2)-Cu thin films: Theoretical and experimental study

In this work the effect of doping concentration and depth profile of Cu atoms on the photocatalytic and surface properties of TiO(2) films were studied. TiO(2) films of about 200 nn thickness were deposited on glass substrates on which a thin Cu layer (5 nm) was deposited. The films were annealed during 1 s to 100 degrees C and 400 degrees C, followed by chemical etching of the Cu film. The grazing incidence X-ray fluorescence measurements showed a thermal induced migration of Cu atoms to depths between 7 and 31 nm. The X-ray photoelectron spectroscopy analysis detected the presence of TiO(2), Cu(2)O and Cu(0) phases and an increasing Cu content with the annealing temperature. The change of the surface properties was monitored by the increasing red-shift and absorption of the ultraviolet-visible spectra. Contact angle measurements revealed the formation of a highly hydrophilic surface for the film having a medium Cu concentration. For this sample photocatalytic assays, performed by methylene blue discoloration, show the highest activity. The proposed mechanism of the catalytic effect, taking place on Ti/Cu sites, is supported by results obtained by theoretical calculations. (C) 2010 Elsevier B.V. All rights reserved.

Spectroscopic and theoretical studies of some 2-ethylsulfinyl-(4 `-substituted)-phenylthioacetates

The analysis of the IR nu(co) bands of the 2-ethylsulfinyl-(4`-substituted)-phenylthioacetates 4`-Y-C(6)H(4)SC(O)CH(2)S(O)Et (Y = NO(2) 1, Cl 2, Br 3, H 4, Me 5, OMe 6) supported by B3LY/6-31G(d,p) calculations along with the NBO analysis for 1.4 and 6 and X-ray analysis for 3, indicated the existence of four gauche (q-g-syn, g(3)-syn. g(1)-atin and q-g(2)-syn) conformers for 1-6 The calculations reproduce quite well the experimental results, i e the computed q-g-syn and g3-syn conformers correspond in the IR spectrum (in solution), to the nu(co) doublet higher frequency component of larger intensity, while the computed grant, conformer correspond to the nu(co) doublet lower frequency component (in solution) NBO analysis showed that the n(s) -> pi(center dot)(c1=o2), no(co) -> sigma(c1-s3), no(co) -> sigma(c1-c4) orbital interactions are the main factors which stabilize the q-g-syn, g(3)-syn, g(1)-anti and q-g(2)-syn conformers for 1, 4 and 6 The no(co) -> sigma(c1-s3) interaction which stabilizes the q-g-syn, g(3)-syn and q-g(2)-syn conformers into a larger extent than the granti conformer, is responsible for the larger tto frequencies of the former conformers relative to the latter one. The q-g-syn, g(3)-syn and q-g(2)-syn conformers are further stabilized sigma(c4-s5) -> pi(co)center dot (strong). pi(co)/sigma(c1-c4,) no(co) -> sigma(c6-H17[Et]) (weak) and pi(co)/sigma(c4-c5) pi(co) (strong) orbital interactions. The q-g-syn conformer is also stabilized by sigma(c4-s5) -> pi(center dot)(co) (strong), pi(co)/sigma(c4-c5).no(co) -> sigma(c6-H17[Et]), pi(C9=C11[ph]) -> sigma(c4-H6x-CH2]) (weak). no((SO)) -> sigma(C11-H23[ph]) (medium) pi(co)/sigma(c4-c5)(strong) orbital interactions. The q-g-syn conformei is further stabilized by the n(S5) O((C))(8-) S((SO))(8+) attractive Coulornbic interaction while the q-g(2)-syn conformer is destabilized by the n55 0,8c-0) repulsive Coulombic interaction. This analysis indicates the following conformer stabilization order. q-g-syn, g(3)-syn > g(1)-anti >> q-g(2)-syn X-ray single crystal analysis of 3 indicates that it assumes in the solid a distorted q-g(2)-syn geometry which is stabilized through almost the same orbital and Coulombic interaction which takes place for the q-g(2)-syn conformer, in the gas, along with dipole moment coupling and a series intermolecular C-HO0 interactions. (C) 2010 Elsevier B V All rights reserved

Conformational preferences for some 2-substituted N-methoxy-N-methylacetamides through spectroscopic and theoretical studies

The analysis of the IR carbonyl band of the 2-substituted N-methoxy-N-methylacetamides Y-CH(2)C(O)-N(OMe)Me (Y = F1, OMe 2, OPh 3, Cl 4), supported by B3LYP/6-311++G(3df, 3pd) calculations along with the NBO analysis for 1-4, indicated the existence of cis-gauche conformers i.e. (c) and (g) for 1 and 3, (c(1), c(2)) and (g(1), g(2)) for 2, and (c) and (g(1), g(2)) for 4. In the gas phase, the g conformer population prevails over the c one, for 1 and 3, the (c(1) + c(2)) population prevails over the (g(1) + g(2)) one for 2, and the (g(1) + g(2)) conformer population is more abundant than (c) one for 4. In n-hexane solution, the cis conformer is more abundant for 1-3. The occurrence of Fermi resonance in the nu(CO) region, in n-hexane, precludes the estimative of relative populations of the (c, g(1), g(2)) conformers for 4. The SCI-PCM calculations agree with the solvent effect on the nu(CO) band component relative intensities for 1-3. NBO analysis showed that the n(N) -> pi.(CO), orbital interaction is the main factor which stabilizes the gauche (g, g(1), g(2)) conformers for 1-4 into a larger extent relative to the cis (c, c(1), c(2)) ones. The n(y) -> pi(.)(Co,) sigma(C-Y) -> pi.(CO,) pi(CO) -> sigma(C-Y) and 7co orbital interactions still contribute, but into a minor extent for the stabilization of the gauche conformers relative to the cis ones. The existence of some pyramidalization at the nitrogen atom of the Weinreb amides 1-4 is responsible for the occurrence of Y(delta)-(4)center dot center dot center dot O(delta)-(9) and Y(delta)-(4)center dot center dot center dot N(delta)-(7) short contacts in the gauche (g, g(1), g(2)) conformers, which originates strong repulsive Coulombic interactions, acting in opposition to the large orbital stabilization of the gauche conformer with respect to the cis one. Therefore, a delicate balance of the Coulombic and orbital interactions seems to be responsible for the observed stabilization of the gauche (g, g(1), g(2)) and cis (c, c(1), c(2)) conformers, both in the gas phase and in the solution for 1-4. However, the cis conformer predominance, in non polar solvents, for the 2-substituted N-methoxy-N-methyl acetamides 1-3, bearing in a first raw (fluorine and oxygen) atoms, is in the opposite direction to the gauche conformer preference for the corresponding 2-substituted N,N-dialkyl-acetamides. (C) 2010 Elsevier B.V. All rights reserved.

The interaction between atoms of Au and Cu with clean Si(111) surface: A study combining synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations

In order to evaluate the interactions between Au/Cu atoms and clean Si(l 11) surface, we used synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations. Optimized geometries and energies on different adsorption sites indicate that the binding energies at different adsorption sites are high, suggesting a strong interaction between metal atom and silicon surface. The Au atom showed higher interaction than Cu atom. The theoretical and experimental data showed good agreement. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

Photocatalytic decomposition of methylene blue via Fenton mechanisms by silicon wafer doped with Au and Cu: a theoretical and experimental study

In this work, we studied the photocatalytic and the structural aspects of silicon wafers doped with Au and Cu submitted to thermal treatment. The materials were obtained by deposition of metals on Si using the sputtering method followed by fast heating method. The photocatalyst materials were characterized by synchrotron-grazing incidence X-ray fluorescence, ultraviolet-visible spectroscopy, X-ray diffraction, and assays of H(2)O(2) degradation. The doping process decreases the optical band gap of materials and the doping with Au causes structural changes. The best photocatalytic activity was found for thermally treated material doped with Au. Theoretical calculations at density functional theory level are in agreement with the experimental data.

A combined X-ray and theoretical study of flavonoid compounds with anti-inflammatory activity

The structure of 7,4`-dimethoxy-3`-acetylflavone (tithonin-Ac) has been determined by X-ray diffraction and its geometry is compared with optimized geometrical parameters obtained by means of density functional theory at the B3LYP/6-311++G(d,p) level of calculation. in addition, vertical ionization potential (IPv) and acidity for tithonin-Ac and two derivatives have been also calculated. Calculations of spin densities were also performed for the radical formed by the electron abstraction of other flavones. The unpaired electron is located on C3 carbon atom (21-25%). (C) 2008 Elsevier B.V. All rights reserved.

A theoretical study on the XeF(2) molecule

A relativistic four-component study was performed for the XeF(2) molecule by using the Dirac-Coulomb (DC) Hamiltonian and the relativistic adapted Gaussian basis sets (RAGBSs). The comparison of bond lengths obtained showed that relativistic effects on this property are small (increase of only 0.01 angstrom) while the contribution of electron correlation, obtained at CCSD(T) or CCSD-T levels, is more important (increase of 0.05 angstrom). Electron correlation is also dominant over relativistic effects for dissociation energies. Moreover, the correlation-relativity interaction is shown to be negligible for these properties. The electron affinity, the first ionization potential and the double ionization potential are obtained by means of the Fock-space coupled cluster (FSCC) method, resulting in DC-CCSD-T values of 0.3 eV, 12.5 eV and 32.3 eV, respectively. Vibrational frequencies and some anharmonicity constants were also calculated under the four-component formalism by means of standard perturbation equations. All these molecular properties are, in general, ill satisfactory agreement with available experimental results. Finally, a partition in terms of charge-charge flux-dipole flux (CCFDF) contributions derived by means of the quantum theory of atoms in molecules (QTAIM) in non-relativistic QCISD(FC)/3-21G* calculations was carried out for XeF(2) and KrF(2). This analysis showed that the most remarkable difference between both molecules lies on the charge flux contribution to the asymmetric stretching mode, which is negligible in KrF(2) but important in XeF(2). (c) 2008 Elsevier B.V. All rights reserved.

Crystal structure and theoretical calculations of Julocrotine, a natural product with antileishmanial activity

Julocrotine, N-(2,6-dioxo-l-phenethyl-piperidin-3-yl)-2-methyl-butyramide, is a potent antiproliferative agent against the promastigote and amastigote forms of Leishmania amazonensis (L.). In this work, the crystal structure of Julocrotine was solved by X-ray diffraction, and its geometrical parameters were compared with theoretical calculations at the B3LYP and HF level of theory. IR and NMR spectra also have been obtained and compared with theoretical calculations. IR absorptions calculated with the B3LYP level of theory employed together with the 6-311G+(d,p) basis set, are close to those observed experimentally. Theoretical NMR calculations show little deviation from experimental results. The results show that the theory is in accordance with the experimental data. (C) 2007 Wiley Periodicals, Inc.

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.

Acoustic Design in Urban Development : analysis of urban soundscapes and acoustic ecology research in New York City

The world is urbanizing rapidly with more than half of the global population now living in cities. Improving urban environments for the well-being of the increasing number of urban citizens is becoming one of the most important challenges of the 21st century. Even though it is common that city planners have visions of a ’good urban milieu’, those visions are concerning visual aesthetics or practical matters. The qualitative perspective of sound, such as sonic diversity and acoustic ecology are neglected aspects in architectural design. Urban planners and politicians are therefore largely unaware of the importance of sounds for the intrinsic quality of a place. Whenever environmental acoustics is on the agenda, the topic is noise abatement or noise legislation – a quantitative attenuation of sounds. Some architects may involve acoustical aspects in their work but sound design or acoustic design has yet to develop to a distinct discipline and be incorporated in urban planning.My aim was to investigate to what extent the urban soundscape is likely to improve if modern architectural techniques merge with principles of acoustics. This is an important, yet unexplored, research area. My study explores and analyses the acoustical aspects in urban development and includes interviews with practitioners in the field of urban acoustics, situated in New York City. My conclusion is that to achieve a better understanding of the human living conditions in mega-cities, there is a need to include sonic components into the holistic sense of urban development.

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.

Learning in and through drama : The necessity to use multiple theoretical perspectives in order to understand how learning takes place in drama

The complexity of learning implies that learning seldom is about just one thing. It can be said that learning processes are interdisciplinary. Within educational contexts, learning is not limited to constructed school subjects. In drama education, learning is simultaneously about drama as aesthetic expression and content because drama always is about something. The mainly focus can be on form, content or social aspects. The different aspects are always present, but may be more or less foreground or the background depending on the purpose of education. How do development concerning understanding of form, content, and social interaction, interact in a learning process in drama? My research is based on the view that learning at the same time takes place as an individual, internal process and a socially situated, inter-subjective process. Can learning in drama imply learning that can be transferred between different situations, a transformative learning and if so, how? Transformative learning includes cognitive, affective and corporal and social action aspects and means that the individual's frames of reference are transformed, evolved, to become more insightful and flexible which implies a change of personality. It leads to an integrated knowledge that can be applied in different contexts.   In the paper that will be presented at the conference, theories about how we learn in drama will be discussed in relation to my empirical research concerning drama and learning.

The Survivability of Swedish Emergency Management Related Research Centers and Academic Programs : A Preliminary Sociology of Science Analysis

The Survivability of Swedish Emergency Management Related Research Centers and Academic Programs: A Preliminary Sociology of Science Analysis Despite being a relatively safe nation, Sweden has four different universities supporting four emergency management research centers and an equal and growing number of academic programs. In this paper, I discuss how these centers and programs survive within the current organizational environment. The sociology of science or the sociology of scientific knowledge perspectives should provide a theoretical guide. Yet, scholars of these perspectives have produced no research on these related topics. Thus, the population ecology model and the notion of organizational niche provide my theoretical foundation. My data come from 26 interviews from those four institutions, the gathering of documents, and observations. I found that each institution has found its own niche with little or no competition – with one exception. Three of the universities do have an international focus. Yet, their foci have minimal overlap. Finally, I suggest that key aspects of Swedish culture, including safety, and a need aid to the poor, help explain the extensive funding these centers and programs receive to survive. 

Thick viewing : empirical examples of condensed moments of narrative impact in fiction film developing theoretical concepts for intensified engagements

Abstract  In a case study about viewing habits in a Swedish audience I sampled 309 questionnaires; interviews with five focus group were conducted together with ten in-depth individual interviews discussing altogether fifteen favorite films exploring specific scenes of idiosyncratic relevance.  The outcome supports claims about viewers as active and playful (cf. Höijer 1998, Frampton 2006, Hoover 2006, Plantinga 2009). In line with mediatization theory I also argue that spiritual meaning making takes place through mediated experiences and I support theories about fiction films as important sources for moral and spiritual reflection (Partridge 2004, Zillman 2005, Lynch 2007, Plantinga 2009). What Hjarvard calls the soft side of mediatization processes (2008) is illustrated showing adults experiencing enchantment through favorite films (Jerslev 2006, Partridge 2008, Klinger 2008, Oliver & Hartmann 2010).  Vernacular meaning making embedded in everyday life and spectators dealing with fiction narratives such as Gladiator, Amelie from Montmartre or Avatar highlights the need for a more nuanced understanding of elevated cinematic experiences. The reported impact of specific movies is analyzed through theories where cognition and affect are central aspects of spectators’ engagements with a film (Tan 1996, Caroll 1999, Grodal 2009). Crucially important are theories of meaning-making where viewers’ detailed interpretation of specific scenes are embedded in high-level meaning-making where world view issues and spectators’ moral frameworks are activated (Zillman 2005, Andersson & Andersson 2005, Frampton 2006, Lynch 2007, Avila 2007, Axelson 2008, Plantinga 2009).  Also results from a growing body of empirical oriented research in film studies are relevant with an interest in what happens with the flesh and blood spectator exposed to filmic narratives (Jerslev 2006, Klinger 2008, Barker 2009, Suckfüll 2010, Oliver & Hartmann 2010). Analyzing the qualitative results of my case study, I want to challenge the claim that the viewer has to suspend higher order reflective cognitive structures in order to experience suture (Butler & Palesh 2004). What I find in my empirical examples is responses related to spectators’ highest levels of mental activity, all anchored in the sensual-emotional apparatus (Grodal 2009). My outcome is in line with a growing number of empirical case studies which support conclusions that both thinking and behavior are affected by film watching (Marsh 2007, Sückfull 2010, Oliver & Hartmann 2010, Axelson forthcoming). The presentation contributes to a development of concepts which combines aesthetic, affective and cognitive components in an investigation of spectator’s moves from emotional evaluation of intra-text narration to extra-textual assessments, testing the narrative for larger significance in idiosyncratic ways (Bordwell & Thompson 1997, Marsh 2007, Johnston 2007, Bruun Vaage 2009, Axelson 2011). There are a several profitable concepts suggested to embrace the complex interplay between affects, cognition and emotions when individuals respond to fictional narratives. Robert K. Johnston label it “deepening gaze” (2007: 307) and “transformative viewing” (2007: 305). Philosopher Mitch Avila proposes “high cognition” (2007: 228) and Casper Thybjerg ”higher meaning” (2008: 60). Torben Grodal talks about “feelings of deep meaning” (Grodal 2009: 149). With a nod to Clifford Geertz, Craig Detweiler adopts “thick description” (2007: 47) as do Kutter Callaway altering it to ”thick interpretations” (Callaway 2013: 203).  Frampton states it in a paradox; ”affective intelligence” (Frampton 2006: 166). As a result of the empirical investigation, inspired by Geertz, Detweiler & Callaway, I advocate thick viewing for capturing the viewing process of these specific moments of film experience when profound and intensified emotional interpretations take place. The author As a sociologist of religion, Tomas Axelsons research deals with people’s use of mediated narratives to make sense of reality in a society characterized by individualization, mediatization and pluralized world views.  He explores uses of fiction film as a resource in every day life and he is currently finishing his three year project funded by the Swedish Research Council: Spectator engagement in film and utopian self-reflexivity. Moving Images and Moved Minds. http://www.du.se/sv/AVM/Personal/Tomas-Axelson Bibliography Axelson, T. (Forthcoming 2014). Den rörliga bildens förmåga att beröra.[1] Stockholm: Liber Axelson, T. (In peer review). Vernacular Meaning Making. Examples of narrative impact in fiction film questioning the ’banal’ notion in mediatization theory. Nordicom Review. Nordicom Göteborg. Axelson, T. (2011). Människans behov av fiktion. Den rörliga bildens förmåga att beröra människan på djupet.[2]Kulturella perspektiv. Volume 2. Article retrieved from www.kultmed.umu.se/digitalAssets/74/74304_axelson-22011.pdf Axelson, Tomas (2010) “Narration, Visualization and Mind. Movies in everyday life as a resource for utopian self-reflection.” Paper presentation at CMRC, 7th Conference of Media, Religion & Culture in Toronto, Canada 9 – 13th August 2010. Axelson, Tomas (2008) Movies and Meaning. Studying Audience, Favourite Films and Existential Matters. Particip@tions : Journal of Audience and Reception Studies. Volume 5, (1). Doctoral dissertation summary. ACTA UNIVERSITATIS UPSALIENSIS. Article retrieved from http://www.participations.org/Volume%205/Issue%201%20-%20special/5_01_axelson.htm  [1] English translation: Moving Images and Moved Minds. [2] English translation: Our need for fiction. Deeply Moved by Moving Images. Cultural Perspectives.