Utilização de RMN de ¹H na determinação da configuração absoluta de álcoois

This review reports the determination of absolute configuration of primary and secondary alcohols by ¹H NMR spectroscopy, using the Mosher method. This method consists in the derivatization of an alcohol possessig unknown absolute configuration with one or both enantiomers of an auxiliary reagent. The resulting diastereoisomer spectra are registered and compared, and the chemical shift differences (DdR,S = deltaR - deltaS) are measured. The determination of the absolute configuration of the alcohol molecule is based on the correlation between its chiral center and the auxiliary reagent's chiral center. Therefore, the determination of the absolute configuration depends on aromatic ring shielding effects on the substituents of the alcohol as evidenced by the ¹H NMR spectrum.

Imaging bilinguals: When the neurosciences meet the languange sciences

The starting point of our investigation was the longstanding notion that bilingual individuals need effective mechanisms to prevent interference from one language while processing material in the other (e.g. Penfield and Roberts, 1959). To demonstrate how the prevention of interference is implemented in the brain we employed event-related brain potentials (ERPs; see Munte, Urbach, ¨ Duzel and Kutas, 2000, for an introductory review) ¨ and functional magnetic resonance imaging (fMRI) techniques, thus pursuing a combined temporal and spatial imaging approach. In contrast to previous investigations using neuroimaging techniques in bilinguals, which had been mainly concerned with the localization of the primary and secondary languages (e.g. Perani, Paulesu, Galles, Dupoux, Dehaene, Bettinardi, Cappa, Fazio and Mehler, 1998; Chee, Caplan, Soon, Sriram, Tan, Thiel and Weekes, 1999), our study addressed the dynamic aspects of bilingual language processing.

Reações de 1,2-dicloro-4,5-dinitrobenzeno com aminas: monossubstituição de nitro e dissubstituição de cloro e nitro

1,2-dichloro-4,5-dinitrobenzene (DCDNB) reacts with primary and secondary amines, in acetonitrile, at room temperature, to give a monosubstituted nitro product with a yield of 85 to 95%. The chloro-nitro-disubstituted product is formed with excess amine under reflux. Piperidine, pyrroline, dimethylamine and methylamine were the most reactive reagents in both mono- and disubstitution.

Actuaciones educativas para la convivencia en centros con alumnado inmigrante

This article shows the results of fieldwork conducted in 11 schools within the project The improvement of living and learning in primary and secondary schools with immigrant students, funded under the National Plan I + D + i (2008-2012). In these schools different educational actions (non-segregation of students in specific groups, organization of host-group-meetings, Coexistence Gatherings or participation of family members) are being carried out, contributing to the improvement of coexistence not only among students but also among families and school professionals.

Estatinas hipolipêmicas e novas tendências terapêuticas

Statins are the most used drugs for the treatment of hyperlipidemia in primary and secondary prevention, with the aim of decreasing the levels of plasmatic cholesterol- lipoproteins. Owing to their structural similarity to the substrate HMG-CoA (3-hydroxy-3-methylglutaryl-CoA), they inhibit the HMG-CoA reductase enzyme, disrupting the cholesterol biosynthesis. Currently, six therapeutic statins are available: lovastatin (Mevacor) and pravastatin (Pravachol), which are natural, sinvastatin (Zocor), a semi-synthetic derivative, and the totally synthetic statins, fluvastatin (Lescol), atorvastatin (Lipitor) and rosuvastatin (Crestor). Recent investigations have showed other important effects of statins, such as antineoplastic action and improvement in endothelial function.

UM MÉTODO EFICIENTE PARA A OBTENÇÃO DE DERIVADOS DE 1-ALQUILAMINO-2,4-DINITROBENZENO E A REDUÇÃO REGIOSSELETIVA PARA A OBTENÇÃO DE DERIVADOS DE 1-ALQUILAMINO-2-AMINO-4-NITROBENZENO

Both primary and secondary amines react with 2,4-dinitrochlorobenzene to give derivatives of 1-alkylamino-2,4-dinitrobenzene. These compounds are important intermediates for the synthesis of a diverse range of products. The methodology reported in the present study involves either the room temperature reaction or heating at 70 °C in ethanol in the presence of triethylamine. This transformation occurs via a nucleophilic substitution reaction. The 1-alkylamino-2,4-dinitrobenzene derivatives were obtained in greater than 90% purified yield. The selective reduction of dinitro compounds is an important synthetic strategy for the synthesis of intermediates for dyes, pharmaceuticals and agrochemicals. The use of SnCl2 as a suspension in EtOAc is a promising method for the regio- and chemo-selective reduction of 1-alkylamino-2,4-dinitrobenzenes to 1-alkylamino-2-amino-4-nitrobenzenes. These products are useful intermediates in organic synthesis.

Jätteenpolton typenoksidipäästöjen vähentäminen

Työn tavoitteena oli selvittää jätteenpolton typenoksidipäästöjen puhdistusmahdollisuuksia. Työssä käydään läpi typen oksidien muodostuminen poltossa ja typen oksidien poistomenetelmät. Poistomenetelmiä käsiteltäessä painotus on arinapoltossa ja erityisesti selektiivisessä ei-katalyyttimenetelmässä (SNCR). Työn kokeellinen osa tehtiin Ekokem Oy Ab:n jätevoimalassa Riihimäellä. Kokeellisessa osassa selvitettiin ensin ammoniakkiveden massavirran, SNCR-laitteiston veden massavirran ja räjähdysnuohouksen vaikutusta typenoksidipitoisuuteen. Samalla selvitettiin muita typenoksidipitoisuuteen vaikuttavia tekijöitä sekä SNCR-laitteiston puhdistustehokkuus. Sen jälkeen selvitettiin parhaita toiminta-arvoja öljyisen veden massavirralle, SNCR-laitteiston massavirralle ja primääri- ja sekundääri-ilman suhteelle typenoksidipitoisuuden, ammoniakki-slip:n, ilokaasupitoisuuden, ammoniakkiveden kulutuksen ja höyryn tuotannon kannalta. Tulokseksi saatiin, että ammoniakkiveden massavirran lisääminen pienentää typenoksidipitoisuutta, mutta voi aiheuttaa ammoniakkipäästön. Paras SNCR-laitteiston veden massavirta on suurin tutkittu, 800 kg/h, jolloin typenoksidipitoisuus sekä typenoksidipitoisuuden hetkittäinen vaihtelu, ammoniakkiveden kulutus ja ammoniakkipäästö ovat pienimmät. Samalla tosin höyryn virtaama pienenee. SNCR-laitteiston puhdistustehokkuudeksi saatiin 60 %. Räjähdysnuohouksella ei ole havaittavaa, eikä öljyisen veden massavirralla merkittävää vaikutusta typenoksidipitoisuuteen. Ammoniakkiveden kulutuksen kannalta paras öljyisen veden määrä on 600 kg/h, kun taas ammoniakki-slip:n kannalta paras öljyisen veden määrä on 950 kg/h. Primääri-ilman osuuden pienentäminen pienentää ammoniakki-slip:iä ja ammoniakkiveden kulutusta.

Video assisted resections. Increasing access to minimally invasive liver surgery?

Objective: To evaluate perioperative outcomes, safety and feasibility of video-assisted resection for primary and secondary liver lesions. Methods : From a prospective database, we analyzed the perioperative results (up to 90 days) of 25 consecutive patients undergoing video-assisted resections in the period between June 2007 and June 2013. Results : The mean age was 53.4 years (23-73) and 16 (64%) patients were female. Of the total, 84% were suffering from malignant diseases. We performed 33 resections (1 to 4 nodules per patient). The procedures performed were non-anatomical resections (n = 26), segmentectomy (n = 1), 2/3 bisegmentectomy (n = 1), 6/7 bisegmentectomy (n = 1), left hepatectomy (n = 2) and right hepatectomy (n = 2). The procedures contemplated postero-superior segments in 66.7%, requiring multiple or larger resections. The average operating time was 226 minutes (80-420), and anesthesia time, 360 minutes (200-630). The average size of resected nodes was 3.2 cm (0.8 to 10) and the surgical margins were free in all the analyzed specimens. Eight percent of patients needed blood transfusion and no case was converted to open surgery. The length of stay was 6.5 days (3-16). Postoperative complications occurred in 20% of patients, with no perioperative mortality. Conclusion : The video-assisted liver resection is feasible and safe and should be part of the liver surgeon armamentarium for resection of primary and secondary liver lesions.

Bone changes caused by experimental Solanum malacoxylon poisoning in rabbits

The aim of this study was to describe the bone changes observed after a daily oral administration of the calcinogenic plant Solanum malacoxylon (syn. S. glaucophyllum) (Sm) during 9 days. The Sm-poisoned rabbits had an increase of bone resorption in the endosteal surface of the cortical zone and also in the surface covered by osteoblasts of the primary and secondary spongiosa of the trabecular bone compartment. Moreover, the epiphyseal growth plates in long bones appeared narrower than in the control rabbits, with reduction of the proliferative and hyperthrophic chondrocyte zones. The electron microscopic study revealed a significant decrease of proteoglycans in the hyperthrophic chondrocyte zone evidenced by a significant reduction of rutenium red positive granules in the poisoned rabbit. Altogether, these data suggest that cell differentiation may play a pivotal role in the pathogenesis of Sm-induced bone lesions.

Supplier codes of conduct: Acting responsibly in global supply chains

Nowadays the Western companies are considered responsible for the social and environmental issues in their whole supply chains. To influence the practices of their suppliers the Western companies have created suppliers codes of conduct (SCCs) which express their requirements. Suppliers’ compliance with the SCCs is checked through audits. The purpose of this thesis is to analyze SCCs as a means for Western companies to ensure socially and environmentally responsible actions in their global supply chains, and the sub-objectives are to find out 1) how well do the SCCs and their auditing work at suppliers’ production sites and 2) how can possible problems related to SCCs and their auditing be solved. This is a qualitative research carried out in the form of a case study with two case companies. In this study both primary and secondary data is used. The primary data is collected in the form of interviews of the case company representatives and three external experts. Based on a theoretical framework of previous research in the fields of corporate social responsibility and supply chain management, a model with eleven factors, which influence the success of SCC implementation and the auditing of SCC –implementation, is drafted. Also several different best-practices to help to solve and avoid possible problems related to SCC -implementation and auditing have been identified from previous research. Based on the findings of this study the theoretical model has been updated adding two new influential factors. It seems that how well the SCC and its auditing work at suppliers’ production sites depends on the joint effect of thirteen influential factors: buyer’s purchasing policy, supplier’s motivation, buyer’s commitment, the solving of agency problems, the contents of the SCC, supplier’s role and the buyer-supplier –relationship, complexity of supply chain, the limitations of the smaller buyers, cooperation through a business association or multi-stakeholder system, the role of supplier’s employees, SCC –related communication and supplier’s understanding, cheating in audits and the auditors. The possible problems related to SCCs and their auditing can be solved by adopting best-practices. Nine of the theoretical best-practices stand out from the findings of this study: 1) two-way communication and collecting feedback from suppliers, 2) the philosophy of continuous improvement, 3) long-term business relationships with the supplier, 4) informing the supplier about the advantages of SCC –compliance, 5) rewarding code-compliant suppliers, 6) building collaborative, good buyer-supplier relationships, 7) supporting and advising the supplier, 8) joining a business association or multi-stakeholder system and 9) interviewing supplier’s employees as a part of the audits.

Wild onion (Asphodelus tenuifolius) competition in rainfed chickpea-chickpea cropping system

Chickpea yield potential is limited by weed competition in typical chickpea growing areas of Pakistan where zero tillage crop grown on moisture conserved from rains received during the months of September and August. The objective of this work was to evaluate the growth and yield characteristics of chickpea grown in coexistence with increasing densities of wild onion (Asphodelus tenuifolius). The experiment was comprised of six density levels viz. zero, 20, 40, 80, 160 and 320 plants m-2 of A. tenuifolius. A decrease in chickpea primary and secondary branches per plant, pods per plant, seeds per pod, 100-seed weight and seed yield was observed due to more accumulation of dry matter per increasing densities of A. tenuifolius. The increase in A. tenuifolius density accelerated chickpea yield losses and reached the maximum values of 28, 35, 42, 50, 58 and 96% at 20, 40, 80, 160 and 320 A. tenuifolius plants m-2, respectively. The yield loss estimation model showed that chickpea losses with infinite A. tenuifolius density were 60%. Yield reduction could be predicted by 2.52% with increase of one A. tenuifolius plant m-2. It is concluded that A. tenuifolius has a strong influence on chickpea seed yield and showed a linear response at the range of densities studied.

The impact of long-term brand development strategies on brand value of companies operating in high-technology markets

The objective of the current research is to investigate brand value generation. The study is conducted in the context of high-technology companies. The research aims at finding the impact of long-term brand development strategies, including advertising investments, R&D investments, R&D intensity, new products developed and design. The empirical part of the study incorporated collection of primary and secondary data on 36 companies operating in high-technology sector and being rated as top companies with the most valuable brands by Interbrand consultancy. The data contained information for six consequent years from 2008 to 2013. Obtained data was analyzed using the methods of fixed effect and random effect model (panel data analysis). The analysis showed positive effect of advertising and R&D investments on brand value of high-technology companies in the long run. The impact of remaining three strategies was not approved and further investigation is required.

One hundred million years of interhemispheric communication: the history of the corpus callosum

Analysis of regional corpus callosum fiber composition reveals that callosal regions connecting primary and secondary sensory areas tend to have higher proportions of coarse-diameter, highly myelinated fibers than callosal regions connecting so-called higher-order areas. This suggests that in primary/secondary sensory areas there are strong timing constraints for interhemispheric communication, which may be related to the process of midline fusion of the two sensory hemifields across the hemispheres. We postulate that the evolutionary origin of the corpus callosum in placental mammals is related to the mechanism of midline fusion in the sensory cortices, which only in mammals receive a topographically organized representation of the sensory surfaces. The early corpus callosum may have also served as a substrate for growth of fibers connecting higher-order areas, which possibly participated in the propagation of neuronal ensembles of synchronized activity between the hemispheres. However, as brains became much larger, the increasingly longer interhemispheric distance may have worked as a constraint for efficient callosal transmission. Callosal fiber composition tends to be quite uniform across species with different brain sizes, suggesting that the delay in callosal transmission is longer in bigger brains. There is only a small subset of large-diameter callosal fibers whose size increases with increasing interhemispheric distance. These limitations in interhemispheric connectivity may have favored the development of brain lateralization in some species like humans. "...if the currently received statements are correct, the appearance of the corpus callosum in the placental mammals is the greatest and most sudden modification exhibited by the brain in the whole series of vertebrated animals..." T.H. Huxley (1).

Modelling Cutting States in Rough Turning of 34CrNiMo6 Steel

Rough turning is an important form of manufacturing cylinder-symmetric parts. Thus far, increasing the level of automation in rough turning has included process monitoring methods or adaptive turning control methods that aim to keep the process conditions constant. However, in order to improve process safety, quality and efficiency, an adaptive turning control should be transformed into an intelligent machining system optimizing cutting values to match process conditions or to actively seek to improve process conditions. In this study, primary and secondary chatter and chip formation are studied to understand how to measure the effect of these phenomena to the process conditions and how to avoid undesired cutting conditions. The concept of cutting state is used to address the combination of these phenomena and the current use of the power capacity of the lathe. The measures to the phenomena are not developed based on physical measures, but instead, the severity of the measures is modelled against expert opinion. Based on the concept of cutting state, an expert system style fuzzy control system capable of optimizing the cutting process was created. Important aspects of the system include the capability to adapt to several cutting phenomena appearing at once, even if the said phenomena would potentially require conflicting control action.

Water chemistry management for future large experimental facilities

The thesis focuses on the water chemistry of the experimental test facilities and their reference VVER reactors. The main objective of the thesis is to provide recommendations for water chemistry management for laboratory facilities (VEERA, PACTEL) simulating the VVERs and for the large future facilities of the Lappeenranta University of Technology. In the beginning, the concept of nuclear power generation and the applicability of the nuclear power usage is discussed. Next, different water chemistry and water purification systems in primary and secondary circuits currently used at the power plant have been outlined. Also the construction geometry and design of test facilities PACTEL and VEERA, as well as the operation principles of their main equipment has been described. Finally, the appropriate water chemistry and water treatment system have been proposed for the existing and future experimental facilities of LUT.