973 resultados para Umpolung, heterocycles, natural products


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Axially chiral substrates are an interesting and widely studied class of compounds as they can be found in bioactive natural products and are employed as functional materials or as ligands in asymmetric catalytic processes. One branch of this family is the well-known world of the atropisomers. Among them, atropisomeric compounds possessing an N–N stereogenic axis are one truthfully fascinating system but not completely understood yet. In this thesis, we computationally investigated the mechanism of the diastereoselective formation of the N – N chiral axis of a hydrazide under asymmetric phase transfer catalytic conditions. Moreover, during this study, torsional barriers have been calculated for both the reagent and the product at the density functional theory (DFT). These values turned out to suitably match the experimental values and observations. Finally, Electronic Circular Dichroism (ECD) spectra have been simulated in order to assign the chiral absolute configuration to the products.

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Dissertation to obtain a Master Degree in Biotechnology

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The theory part of the Master’s thesis introduces fibres with high tensile strength and elongation used in the production of paper or board. Strong speciality papers are made of bleached softwood long fibre pulp. The aim of the thesis is to find new fibres suitable for paper making to increase either tensile strength, elongation or both properties. The study introduces how fibres bond and what kind of fibres give the strongest bonds into fibre matrix. The fibres that are used the in manufacturing of non-wovens are long and elastic. They are longer than softwood cellulose fibres. The end applications of non-wovens and speciality papers are often the same, for instance, wet napkins or filter media. The study finds out which fibres are used in non-wovens and whether the same fibres could be added to cellulose pulp as armature fibres, what it would require for these fibres to be blended in cellulose, how they would bind with cellulose and whether some binding agents or thermal bonding, such as hot calendaring would be necessary. The following fibres are presented: viscose, polyester, nylon, polyethylene, polypropylene and bicomponent fibres. In the empiric part of the study the most suitable new fibres are selected for making hand sheets in laboratory. Test fibres are blended with long fibre cellulose. The test fibres are viscose (Tencel), polypropylene and polyethylene. Based on the technical values measured in the sheets, the study proposes how to continue trials on paper machine with viscose, polyester, bicomponent and polypropylene fibres.

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This study aimed to evaluate the use of rosemary (Rosmarinus officinalis) extract (RE), celery (Apium graveolis), and low levels of NO3 and NO2 as natural agents to enhance the quality of colonial salami. Salami was produced according to three treatments: (A) Control: 0.1% curing salt; (B) Rosemary: 0.05% curing salt + 0.5% RE (rosemary extract); and (C) Rosemary+celery: 0.14% Veg 503 + 0.27% Veg 504 (sea salt plus celery) + 0.5% of RE (rosemary extract). There was no effect (P > 0.05) of the treatments on water activity, Na content, and residual NO3 and NO2. Fatty acids C18:2 and C20:4 were reduced (P < 0.05) during the ripening period in the Control treatment indicating possible oxidation. The use of celery resulted in lower pH values (P < 0.05) in the salami. Reduced addition of NO3 and NO2 resulted in salami lighter in color (higher L* values, P < 0.05) at the 12th day of ripening. In conclusion, celery-based products proved to be an effective source of NO2 and NO3 for color development, but the low pH of the product indicates the need for better evaluation of its use in fermented salami. The RE (rosemary extract) reduced fat oxidation in salami, but this needs further evaluation.

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School of Industrial Fisheries, Cochin University of Science and Technology

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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(Photo)electrochemical experiments on pyrite electrodes in acetic acid-acetate buffer (pH = 4.5) are conducted to clarify the main oxidation reactions and the nature of the products. Electrochemical reactions in the -0.40 to 1.25 V (SHE) potential range are studied, and the production of iron (III) polysulfide from anodically formed iron oxides and polysulfides is discussed. Charges experimentally obtained are considered for the estimation of the most likely stoichiometry of the metallic polysulfide. The photoselectivity of the pyrite corrosion process indicates that the oxidation reactions of Fe2+ and S-2(2-) an not consecutive. The changes in stoichiometry and/or annihilation of crystalline structure defects are responsible for the observed photosensitivity of pyrite. A description of light effects on the interfacial behaviour and stability of pyrite is presented in terms of conduction and valence band energies, and thermodynamic potentials. (C) 2001 Elsevier Science B.V. All rights reserved.

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"First edition 1907 ... Third impression 1911."

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Purpose: To evaluate the comparative efficiency of graphite furnace atomic absorption spectrometry (GFAAS) and hydride generation atomic absorption spectrometry (HGAAS) for trace analysis of arsenic (As) in natural herbal products (NHPs). Method: Arsenic analysis in natural herbal products and standard reference material was conducted using atomic absorption spectrometry (AAS), namely, hydride generation AAS (HGAAS) and graphite furnace (GFAAS). The samples were digested with HNO3–H2O2 in a ratio of 4:1 using microwaveassisted acid digestion. The methods were validated with the aid of the standard reference material 1515 Apple Leaves (SRM) from NIST Results: Mean recovery of three different samples of NHPs, using HGAAS and GFAAS, ranged from 89.3 - 91.4 %, and 91.7 - 93.0 %, respectively. The difference between the two methods was insignificant. A (P= 0.5), B (P=0.4) and C (P=0.88) Relative standard deviation (RSD) RSD, i.e., precision was 2.5 - 6.5 % and 2.3 - 6.7 % using HGAAS and GFAAS techniques, respectively. Recovery of arsenic in SRM was 98 and 102 % by GFAAS and HGAAS, respectively. Conclusion: GFAAS demonstrates acceptable levels of precision and accuracy. Both techniques possess comparable accuracy and repeatability. Thus, the two methods are recommended as an alternative approach for trace analysis of arsenic in natural herbal products.

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Reduction of the natural sesquiterpene lactones furanoheliangolides with Stryker's reagent is an effective process for producing eremantholides through a biomimetic pathway. Other reduction products are also formed. Oxygenated functions at C-15 of the furanoheliangolide produce an increase in the velocities of the reactions and reduce the chemoselectivity of the reagent.