Detailed analysis of the charge transfer complex N,N-dimethylaniline-SO(2) by Raman spectroscopy and density functional theory calculations

Although the amine sulfur dioxide chemistry was well characterized in the past both experimentally and theoretically, no systematic Raman spectroscopic study describes the interaction between N,N-dimethylaniline (DMA) and sulfur dioxide (SO(2)). The formation of a deep red oil by the reaction of SO(2) with DMA is an evidence of the charge transfer (CT) nature of the DMA-SO(2) interaction. The DMA -SO(2) normal Raman spectrum shows the appearance of two intense bands at 1110 and 1151 cm(-1), which are enhanced when resonance is approached. These bands are assigned to nu(s)(SO(2)) and nu(phi-N) vibrational modes, respectively, confirming the interaction between SO(2) and the amine via the nitrogen atom. The dimethyl group steric effect favors the interaction of SO(2) with the ring pi electrons, which gives rise to a pi-pi* low-energy CT electronic transition, as confirmed by time-dependent density functional theory (TDDFT) calculations. In addition, the calculated Raman DMA-SO(2) spectrum at the B3LYP/6-311++g(3df,3pd) level shows good agreement with the experimental results (vibrational wavenumbers and relative intensities), allowing a complete assignment of the vibrational modes. A better understanding of the intermolecular interactions in this model system can be extremely useful in designing new materials to absorb, detect, or even quantify SO(2). Copyright (C) 2009 John Wiley & Sons, Ltd.

Computer-aided Structure Elucidation of Neolignans

This paper describes a new module of the expert system SISTEMAT used for the prediction of the skeletons of neolignans by (13)C NMR, (1)H NMR and botanical data obtained from the literature. SISTEMAT is composed of MACRONO, SISCONST, C13MACH, H1MACH and SISOCBOT programs, each analyzing data of the neolignan in question to predict the carbon skeleton of the compound. From these results, the global probability is computed and the most probable skeleton predicted. SISTEMAT predicted the skeletons of 75% of the 20 neolignans tested, in a rapid and simple procedure demonstrating its advantage for the structural elucidation of new compounds.

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.

Structural Investigation of MFe(2)O(4) (M = Fe, Co) Magnetic Fluids

Ferrites of the type M(II)Fe(2)O(4) (M = Fe and Co) have been prepared by the traditional coprecipitation method. These ferrites were modified by the adsorption of fatty acids derived from soybean and castor oil and were then dispersed in cyclohexane, providing very stable magnetic fluids, readily usable in nonpolar media. The structural properties of the ferrites and modified ferrites as well as the magnetic fluids were characterized by XRD (X-ray powder diffraction), TEM (transmission electron microscopy), DRIFTS (diffusion reflectance infrared Fourier transform spectroscopy), FTMR (Fourier transform near-infrared), UV-vis, normal Raman spectroscopy, and surface-enhanced Raman scattering (SERS). XRD and TEM analysis have shown that the magnetic nanoparticles (nonmodified and modified) present diameters in the range of 10-15 nm. DRIFTS measurements have shown that the carboxylate groups of soybean and castor oil fatty acids adsorb on the ferrite surface, forming three different structures: a bridging bidentate, a bridging monodentate, and a bidentate chelate structure. The FTIR and Raman spectra of nonmodified Fe(3)O(4) and CoFe(2)O(4) nanoparticles have shown that the number of observed phonons is not compatible with the expected O(h)(7) symmetry, since IR-only active phonons were observed. in the Raman spectra and vice versa. SERS measurements of a CoFe(2)O(4) thin film on a SERS-active gold electrode at different applied potentials made possible the assignment of the signals near 550 and 630 cm(-1) to Co-O motions and the signals near 470 and 680 cm(-1) to Fe-O motions.

In vitro Trypanocidal Activity of Phenolic Derivatives from Peperomia obtusifolia

The trypanocidal activity of crude extracts and fractions from the leaves and stems of Peperomia obtusifolia (Piperaceae) was evaluated in vitro against the epimastigote forms of Trypanosoma cruzi. Bioactivity-guided fractionation of the most active extracts afforded seven known compounds, including three chromanes, two furofuran lignans and two flavone C-diglycosides. The most active compounds were the chromanes peperobtusin A and 3,4-dihydro-5-hydroxy-2,7-dimethyl-8-(2 ``-methyl-2 ``-butenyl)-2-(4`-methyl-1`,3`-pentadienyl)-2H-1-benzopyran-6-carboxylic acid, with IC(50) values of 3.1 mu M (almost three times more active than the positive control benznidazole, IC(50) 10.4 mu M) and 27.0 mu M, respectively. Cytotoxicity assays using peritoneal murine macrophages indicated that the chromanes were not toxic at the level of the IC(50) for trypanocidal activity. This is the first report on the trypanocidal activity besides unspecific cytotoxicity of chromanes from Peperomia species. Additionally it represents the first time isolation of 3,4-dihydro5-hydroxy-2,7-dimethyl-8-(2 ``-methyl-2 ``-butenyl)-2-(4`-methyl-1`,3`-pentadienyl)-2H-1-benzopyran-6-carboxylic acid from P. obtusifolia.

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.

Surface-enhanced Raman study of electrochemical and photocatalytic degradation of the azo dye Janus Green B

The photocatalytic degradation of Janus Green B azo dye over silver modified titanium dioxide films was investigated by surface-enhanced Raman spectroscopy (SERS). An optimized SERS-active substrate was employed to study the photodegradation reaction of Janus Green B. Considering that photocatalytic degradation processes of organic molecules adsorbed on TiO2 might involve either their oxidation or reduction reaction, the vibrational spectroelectrochemical study of the dye was also performed, in order to clarify the transformations involved in initial steps of its photochemical decomposition. In order to understand the changes in Raman spectra of Janus Green B after photodegradation and/or electrochemical processes, a vibrational assignment of the main Raman active modes of the dye was carried out, based on a detailed resonance Raman profile. Products formed by electrochemical and photochemical degradation processes were compared. The obtained results revealed that the first steps of the degradation process of Janus Green B involve a reductive mechanism. (C) 2007 Published by Elsevier B.V.

Metabolomic assessment with CE-MS of the nutraceutical effect of Cystoseira spp extracts in an animal model

There is a need of scientific evidence of claimed nutraceutical effects, but also there is a social movement towards the use of natural products and among them algae are seen as rich resources. Within this scenario, the development of methodology for rapid and reliable assessment of markers of efficiency and security of these extracts is necessary. The rat treated with streptozotocin has been proposed as the most appropriate model of systemic oxidative stress for studying antioxidant therapies. Cystoseira is a brown alga containing fucoxanthin and other carothenes whose pressure-assisted extracts were assayed to discover a possible beneficial effect on complications related to diabetes evolution in an acute but short-term model. Urine was selected as the sample and CE-TOF-MS as the analytical technique to obtain the fingerprints in a non-target metabolomic approach. Multivariate data analysis revealed a good clustering of the groups and permitted the putative assignment of compounds statistically significant in the classification. Interestingly a group of compounds associated to lysine glycation and cleavage from proteins was found to be increased in diabetic animals receiving vehicle as compared to control animals receiving vehicle (N6, N6, N6-trimethyl-L-lysine, N-methylnicotinamide, galactosylhydroxylysine, L-carnitine, N6-acetyl-N6-hydroxylysine, fructose-lysine, pipecolic acid, urocanic acid, amino-isobutanoate, formylisoglutamine. Fructoselysine significantly decreased after the treatment changing from a 24% increase to a 19% decrease. CE-MS fingerprinting of urine has provided a group of compounds different to those detected with other techniques and therefore proves the necessity of a cross-platform analysis to obtain a broad view of biological samples.

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

Dereplication of Bromotyrosine-derived Metabolites by LC-PDA-MS and Analysis of the Chemical Profile of 14 Aplysina Sponge Specimens from the Brazilian Coastline

In order to investigate the chemical profile of 14 specimens of Aplysina spp. marine sponges, we have developed a method based on LC-PDA-MS for the detection of bromotyrosine-derived metabolites. The method enabled the dereplication of three distinct chemotypes of bromotyrosine-derived compounds based on UV absorptions, which were further refined by electrospray ionization-mass spectrometry analysis of the brominated quasi-molecular ion clusters. This procedure led to either a single compound assignment, or a maximum of two possible isobaric compounds. The dereplication study indicated that the chemical profile of the 14 specimens of Aplysina spp. analyzed presented practically the same dibromotyrosine-derived compounds. The results obtained suggested a possible biogenetic pathway for the formation of dibromotyrosine-derived compounds of wide occurrence in Verongida sponges.

Design Management för Remote Control Sweden AB

This Degree Project is a cooperativ work with the advertising agency PAX in Falun and the industrial companyRemote Control, who constructs and sells actuators for the global market.The assignment concerns bringing out a graphic profile, or with another expression a Design Management, forRemote Control AB graphic materials. Remote Control AB has a quality certification ISO 9000 and is workingwith, when this report was wrote, an environment certification ISO 14001.The Company has been paid attention to Internet and other media.The supervisors are familiar to that Design Management is a soon coming competition element, like quality andenvironment management.This Degree project contains research, analysis and the construction of graphic material. The research has beencommitted most of the time to trace the customer, the market and the competitor, because its the most importantphase. It’s also important looking at competitor’s way of working with marketing management, so you can separatethem from the own company.

Bättre utnyttjande av nya och befintliga förrådslokaler på SSAB Tunnplåt

The purpose of this assignment at SSAB Tunnplåt in Borlänge was mainly to investigate and describe the circumstances for the spare parts stored in storage facilities within the area of operation. Even new facilities which could serve as storage rooms and their opportunities for storing spare parts were an important part of the investigation. This because of the need for improved storing of spare parts. Furthermore, market offers where reviewed for storage of spare parts in more tailored designs. The work will culminate in proposals for improvement which is of importance for the development surrounding the storage and handling of spare parts. This is since the design and management of existing storage facilities is not perceived as satisfactory with regards to spare parts characteristics. Moreover, the amount of stock locations is too few in relation to the actual need. The approach used to achieve objectives of the work was an advanced mapping for collection of vital data. The mapping consisted of interviews with involved parties, both internal and external, for the most comprehensive picture of the problems as possible. In addition, a literature survey was conducted to identify possible options for the objectives of the work as well as a personal study of existing and new storage facilities. Furthermore, the market offers for improved conditions in storage rooms were examined. A clear picture of internal logistics and warehouse activities for spare parts at SSAB Tunnplåt has been obtained during this work. From this picture, it is concluded that work in and around storage facilities can be made more efficient. SSAB Tunnplåt should additionally make efforts in the storage facilities for better use of the available storage space. A number of proposals for improvement for each studied storage facility and spare parts management in general have been conducted. These proposals for improvement include presentations to improve the design of the studied storage facilities towards enabling more stock locations. The proposals also include additional equipment for handling spare parts, scrap handling, as well as expansions of the maintenance system which supports activities in the spare parts management.

Variabeltryck med inkjet i dagspress : Möjligheten att införa anpassade upplagor

På uppdrag av Tidningsutgivarna har en studie utförts angående olika möjligheter att införa tryck av variabeldata med tryckmetoden inkjet i svensk dagspress. Målet var att undersöka tekniska möjligheter och begränsningar samt att utreda om det fanns något intresse på marknaden som skulle kunna ge någon avkastning. Studien utfördes med hjälp av noggranna källstudier och ett fortlöpande samarbete med olika företag med intresse för dagspress. Rapporten beskriver också företag som arbetar med den här typen av innovationer idag och diverse tidigare projekt med variabeltryckta tidningar. Nya teknologier som eventuellt kan vara av intresse för framtida utveckling har också beskrivits och hur tidningens framtid kommer att se ut ur ett kortare och ett längre perspektiv. Studien visar att inkjetpressar inte klarar av den hastighet som de moderna tidningspressarna håller idag. Men i takt med minskade upplagor och utvecklad teknologi, samt ett stort marknadsmässigt intresse så tyder det på att det kommer att finnas möjlighet att tillverka anpassade digitaltryckta tidningsupplagor inom en överskådlig framtid. Inkjet kan fungera som ett bra komplement till offset. Inlinepressar ger möjligheten att införa variabeltryck i stora tidningsupplagor medan separata inkjetpressar passar bra för tryck av mindre lokala upplagor.

Matematikläxans fördelar och nackdelar : En intervjustudie av lärares syn på matematikläxor i grundskolans tidigare år

Syftet med denna studie är att få kunskap om lärares syn på matematikläxor i grundskolans tidigare år. Förhoppningen var att få förståelse för lärares syfte med matematikläxor och vilka förmågor eleverna förväntas utveckla med matematikläxors hjälp samt att jämföra vilka för- och nackdelar matematikläxan har. För att undersöka detta har sju intervjuer gjorts med lärare från olika skolor och olika årskurser från 1-6. Samtliga lärare som intervjuats undervisar i matematik. Lärares erfarenheter av läxornas betydelse för matematikundervisningen är ett viktigt område att få kunskap om. De lärare som deltog i intervjuerna uttryckte olika synpunkter på matematikläxan. Något lärarna var överens om var att läxa är en skoluppgift som eleven tar med hem efter skolans slut och arbetar med hemma. Lärarna uttryckte samstämmigt att eleverna inte utvecklar några förmågor med matematikläxans hjälp utan förmågorna utvecklar eleverna i skolan med hjälp av lärarna. Det framgick att samtliga lärare upplevde att matematikläxan var tidskrävande och för att matematikläxan ska nå syftet på bästa möjliga sätt behövs mer tid. Att läxan kopplas till undervisning och uppföljning är centralt för att syftet med matematikläxan ska uppnås enligt de intervjuade lärarna. Av resultaten framgår att några lärare är negativt inställda till matematikläxor för att uppföljning och koppling till undervisningen inte finns med och därför förlorar matematikläxan sitt syfte. Föräldrarnas förutsättningar är väldigt olika som exempelvis att de har svårigheter med det svenska språket eller inte är engagerade i barnets skolgång. Andra lärare är positivt inställda till matematikläxor för att färdighetsträningen och repetitionen är viktig och tiden som behövs för det inte räcker till i skolan.

Optimization heuristic solutions, how good can they be? : With empirical applications in location problems

Combinatorial optimization problems, are one of the most important types of problems in operational research. Heuristic and metaheuristics algorithms are widely applied to find a good solution. However, a common problem is that these algorithms do not guarantee that the solution will coincide with the optimum and, hence, many solutions to real world OR-problems are afflicted with an uncertainty about the quality of the solution. The main aim of this thesis is to investigate the usability of statistical bounds to evaluate the quality of heuristic solutions applied to large combinatorial problems. The contributions of this thesis are both methodological and empirical. From a methodological point of view, the usefulness of statistical bounds on p-median problems is thoroughly investigated. The statistical bounds have good performance in providing informative quality assessment under appropriate parameter settings. Also, they outperform the commonly used Lagrangian bounds. It is demonstrated that the statistical bounds are shown to be comparable with the deterministic bounds in quadratic assignment problems. As to empirical research, environment pollution has become a worldwide problem, and transportation can cause a great amount of pollution. A new method for calculating and comparing the CO2-emissions of online and brick-and-mortar retailing is proposed. It leads to the conclusion that online retailing has significantly lesser CO2-emissions. Another problem is that the Swedish regional division is under revision and the border effect to public service accessibility is concerned of both residents and politicians. After analysis, it is shown that borders hinder the optimal location of public services and consequently the highest achievable economic and social utility may not be attained.