Produção e caracterização de espumas cerâmicas obtidas a partir de lodo de anodização de alumínio

Ceramic foams were produced from a sludge generated in the aluminum anodizing process by using an industrial polyurethane foam (replication method) with open cell sizes of 10 ± 5 ppi (porosity = 97%) which were impregnated with suspensions containing 50-61 wt.% alumina, 1 wt.% citric acid, 6 wt.% bentonite and fired at 1600 ºC for 2 h. The aluminum anodizing sludge shows a high alumina content (87.5 wt.%) and a low particle size (~1.7 mm) after calcination and milling. The obtained filters show porosity of approximately 70%, filtration capability (mass water flow) of 1.7 kg/s and mechanical strength under compression of 2.40 MPa.

The contributions of Henri Victor Regnault in the context of organic chemistry of the first half of the nineteenth century

A very little known aspect of the scientific career of Regnault is his contribution to the emerging organic chemistry in the first half of the nineteenth century. The purpose of this article is not only to describe two of his most important researches in this field, as were the discovery of two series of halogenated derivates of certain organic compounds and the precise identification of some of the then recently discovered alkaloids, but also the main features that identified his research method. With the involvement in these subjects, Regnault unintentionally positioned himself in the midst of some of the polemics about the classification of organic compounds that characterized this age of science.

Constituintes químicos e avaliação da atividade antibacteriana de Macroptilium lathyroides (L.) Urb. (Fabaceae)

The chemical investigation of the stems and branches of Macroptilium lathyroides led to the isolation of a mixture of β-sitosterol and stigmasterol. The extracts from the roots allowed the isolation of lasiodiplodin, a mixture of stigmast-4-en-6β-ol-3-one and stigmast-4,22-dien-6β-ol-3-one, de-O-methyllasiodiplodin, genistein and lupinalbin A. The structures of the isolated compounds were assigned on the basis of their NMR data, including comparison of their spectral data with values described in the literature. The antibacterial activity of crude extracts from stems, branches and roots was evaluated. This is the first report involving the chemical investigation of this species.

Desenvolvimento do método de extração sólido-líquido com partição em baixa temperatura para determinação de inseticidas em grãos de milho ozonizados

The objective of this study was to optimize and validate a solid-liquid extraction method with low-temperature partitioning (SLE/LTP) for the analysis of pesticides. This method was coupled with gas chromatography (GC/ECD) and used to evaluate the degradation of bifenthrin and pirimiphos-methyl in maize grains on exposure to ozone. The optimized SLE/LTP-GC/ECD method is simple, effective and consumes low quantities of the solvent. It can be routinely used for the determination of bifenthrin and pirimiphos-methyl in maize samples. The use of this method of analysis determined that the levels of the insecticides in maize grains were reduced on exposure of the grains to the ozone gas. The observed reduction in the levels of insecticide was directly proportional to the increase in the concentration of the ozone gas.

Otimização e validação da extração sólido-líquido e purificação em baixa temperatura de HPAs em lodo de esgoto

In this study, a method of solid-liquid extraction and purification at low temperature (SLE-PLT) to determine 16 polycyclic aromatic hydrocarbons (PAHs) in sewage sludge was optimized and validated. The analyses were performed by HPLC-UV. The extraction phase, homogenization procedure, influence of pH, ionic strength and clean-up of the extracts were optimized. Recoveries were higher than 63.4% for 11 PAHs. The correlation coefficients were greater than 0.99 and limits of detection and quantitation were less than 0.060 and 0.15 µg g-1, respectively. These values were lower than the maximum residue limits of PAHs established by European legislation. SLE-PLT proved a more practical, economical method with fewer steps compared to Soxhlet extraction (reference method) for PAHs in sewage sludge.

MONITORAMENTO DE RESÍDUOS DE AGROTÓXICOS DA CLASSE DOS ORGANOFOSFORADOS POR CGDFC EM AMOSTRAS DE LEITE FLUÍDO E EM PÓ

Samples of whole fluid pasteurized, UHT and powdered milk were analyzed for the presence of organophosphorus pesticide residues (OPR) using the QuEChERS method with detection by GC-FPD and confirmation by UPLC-MS/MS. A total of 23% of fluid milk samples and 27% of powdered milk samples contained at least one organophosphorus residue. The OPR found in the samples showed these can reach the milk and remain even after pasteurization, sterilization and drying processes. Some domestic sanitary residues were also present in the powdered milk samples. These residues have no LMR in Brazilian food legislation and are therefore not taken into account in food intake evaluations. There was an unidentified chromatographic peak in 30% of all the liquid and powdered milk samples, indicating the presence of some other contaminant.

Ultrakevyen rahtialuksen kansiluukkujen sekä luukkujen siirto- ja varastointijärjestelmän suunnittelu hyödyntäen kevytrakennekonsepteja

Tämän työn tarkoituksena oli tutkia miten rahtialuksen kansiluukut voitaisiin valmistaa mahdollisimman kevyiksi. Katettavan ruuman pinta-ala on n. 10 m x 40 m. Luukkujen suuresta jännevälistä johtuen, rakenteelta vaaditaan suurta jäykkyyttä. Erilaisina vaihtoehtoina tutkittiin vaahtomaista alumiinia, alumiinisia kennorakenteita ja polyuretaanisia sandwich-rakenteita. Työssä vertailtiin myös erilaisia geometrisia ratkaisuja, joilla kansiluukkujen jäykkyyttä pyrittiin lisäämään ja sitä kautta pääsemään pienempään materiaalin tarpeeseen. Geometriaa suunniteltaessa huomioitiin myös vaikutukset ruuman tilavuuteen ja lainsäädännön asettamat reunaehdot. Lainsäädännöstä saatiin esimerkiksi turvakaiteiden minimikorkeus, joka vaikuttaa suoraan ruuman tilavuuteen, kun aluksen korkeimmaksi kohdaksi on valittu laivan keskilinja ja tämä korkeus on annettu suunnittelun lähtötietona. Tietokoneavusteisen lujuuslaskennan avulla eri vaihtoehdoista muodostettiin elementtimallit. Malleja varioimalla ja tuloksia vertailemalla saatiin selville kevyin mahdollinen rakenne ja geometria. Malleista saatiin selville myös luukkujen tukireaktiovoimat, eli voimat, jotka luukut kohdistavat aluksen muihin rakenteisiin. Lisäksi työssä mietittiin erilaisia tapoja ruuman avaamiseen ja avaamistavan vaikutusta kansiluukkujen painoon, geometriaan ja ruuman tilavuuteen.

Kokeellisen moodianalyysin jälkikäsittely ominaismuotojen visuaaliseksi tarkastelemiseksi

Kokeellinen moodianalyysi on kokeellinen menetelmä, jolla voidaan selvittää rakenteille ominaista värähtelyä. Työssä oli kolme tavoitetta, jotka pyrittiin saavuttamaan. Ensimmäinen tavoite oli ohjeistuksen luominen rakenteiden ominaismuotojen visuaaliseksi tarkastelemiseksi Lappeenrannan teknillisellä yliopistolla käytettävissä olevilla laitteistoilla ja ohjelmilla. Ohjeistuksen perustana on ajatus siitä, että kokeellinen moodianalyysi saataisiin tehokkaampaan käyttöön koneensuunnittelun opetuksessa. Ohjeistus tehtiin pääasiassa kuvien ja kuvia tukevien selitysten avulla. Työn toisena tavoitteena oli verrata rakenteen ominaisvärähtelyä, kun se oli tuettu vapaasti ja kun se oli tuettu kiinteästi sen luonnolliseen ympäristöön. Taajuuksia verrattaessa huomattiin, että eri tavoin tuetut rakenteet käyttäytyvät eri tavalla, mikä on otettava huomioon, kun tutkitaan kriittisiä värähtelyjä. Ominaisvärähtelyjä voidaan selvittää myös matemaattisesti esimerkiksi äärellisten elementtien menetelmällä. Työn kolmantena tavoitteena oli verrata elementtimenetelmällä ja kokeellisesti saatuja ominaisvärähtelyn arvoja. Elementtimallia pyrittiin tarkentamaan eri parametrejä muuttamalla niin, että ominaistaajuuksien arvot vastaavat mahdollisimman hyvin toisiaan. Tavoite saavutettiin.

Ultralujasta teräksestä valmistetun liitoksen pienahitsin staattinen kestävyys

Ultralujat teräkset ovat teräksiä, joiden lujuus on reilusti suurempi verrattuna perinteisiin rakenneteräksiin. Niiden ominaisuuksia hyödynnetään eniten nosto- ja kuljetusvälinete¬ollisuudessa. Ultralujien terästen käyttö avaa suunnittelijalle uusia mahdollisuuksia suun¬nitella ulottuvampia ja kevyempiä rakenteita, jolloin voidaan saavuttaa säästöjä niin val¬mistus- kuin polttoainekustannuksissakin. Ultralujille teräksille ei kuitenkaan ole ole¬massa niitä vastaavia suunnitteluohjeita tai standardeja. Teräsrakenteiden liitosten suun¬nitteluun mitoitusohjeita antava standardi SFS-EN 1993-1-8 ei huomioi teräksiä, joiden myötölujuus on yli 460 MPa. SFS-EN 1993-1-12 on 1993-1-8:n laajennus, joka on voi¬massa myötölujuuteen 700 MPa asti. Tässä diplomityössä tutkittiin ultralujista teräksistä valmistettujen pienahitsiliitosten käyttäytymistä vetokokeiden ja elementtimenetelmän avulla. Tulosten avulla voitiin mää¬rittää matalalujuuksisten terästen mitoitusohjeiden soveltuvuutta ultralujille teräksille. Kokeissa käytetty teräs oli Ruukin valmistama Optim 960 QC.

Covalent anion of Li(HF)3- system: an ab initio study

In this paper, we report the stability of the Li(HF)3- molecular anion calculated at the MP2/6-31++G** and CCSD(T)/6-31++G** level of theory. Five possible conformers of Li(HF)3- molecular anions have been determined employing ab initio MP2 method with 6-31++G** basis set. The most stable conformer of five Li(HF)3- anions is in a cyclic ring structure Li(HF)3-(1). From our calculations we show that the molecule is stable towards electron attachment, with an electron adiabatic electron affinity (AEA) of 199.5 meV (233.1 meV with zero point energy correction) and 471.3 meV at the MP2 and CCSD(T) levels, respectively. In addition we present vertical detachment energies of 230.2 meV and 795.8 meV at the MP2, CCSD(T), respectively. The importance of the latter has to do with the ability of experimental detection of this value.

Flow-batch analyser for preparation of calibration standard mixtures in simultaneous multicomponent spectrometric analysis

The application of multivariate calibration techniques to multicomponent analysis by UV-VIS molecular absorption spectrometry is a powerful tool for simultaneous determination of several chemical species. However, when this methodology is accomplished manually, it is slow and laborious, consumes high amounts of reagents and samples, is susceptible to contaminations and presents a high operational cost. To overcome these drawbacks, a flow-batch analyser is proposed in this work. This analyser was developed for automatic preparation of standard calibration and test (or validation) mixtures. It was applied to the simultaneous determination of Cu2+, Mn2+ and Zn2+ in polyvitaminic and polymineral pharmaceutical formulations, using 4-(2-piridilazo) resorcinol as reagent and a UV-VIS spectrophotometer with a photodiode array detector. The results obtained with the proposed system are in good agreement with those obtained by flame atomic absorption spectrometry, which was employed as reference method. With the proposed analyser, the preparation of calibration and test mixtures can be accomplished about four hours, while the manual procedure requires at least two days. Moreover, it consumes smaller amounts of reagents and samples than the manual procedure. After the preparation of calibration and test mixtures, 60 samples h-1 can be carried out with the proposed flow-batch analyser.

Synthesis and characterization of Fe(III)-doped ceramic membranes of titanium dioxide and its application in photoelectrocatalysis of a textile dye

Pure and Fe(III)-doped TiO2 suspensions were prepared by the sol gel method with the use of titanium isopropoxide (Ti(OPri)4) as precursor material. The properties of doped materials were compared to TiO2 properties based on the characterization by thermal analysis (TG-DTA and DSC), X-ray powder diffractometry and spectroscopy measurements (FTIR). Both undoped and doped TiO2 suspensions were used to coat metallic substrate as a mean to make thin-film electrodes. Thermal treatment of the precursors at 400ºC for 2 h in air resulted in the formation of nanocrystalline anatase TiO2. The thin-film electrodes were tested with respect to their photocatalytic performance for degradation of a textile dye in aqueous solution. The plain TiO2 remains as the best catalyst at the conditions used in this report.

Biochemical Modification of Thermomechanical Pulp Fibers

The first objective of this study was to find out reliable laboratory methods to predict the effect of enzymes on specific energy consumption and fiber properties of TMP pulp. The second one was to find with interactive software called “Knowledge discovery in databases” enzymes or other additives that can be used in finding a solution to reduce energy consumption of TMP pulp. The chemical composition of wood and enzymes, which have activity on main wood components were presented in the literature part of the work. The results of previous research in energy reduction of TMP process with enzymes were also highlighted. The main principles of knowledge discovery have been included in literature part too. The experimental part of the work contains the methods description in which the standard size chip, crushed chip and fiberized spruce chip (fiberized pulp) were used. Different types of enzymatic treatment with different dosages and time were tested during the experiments and showed. Pectinase, endoglucanase and mixture of enzymes were used for evaluation of method reliability. The fines content and fiber length of pulp was measured and used as evidence of enzymes' effect. The refining method with “Bauer” laboratory disc refiner was evaluated as not highly reliable. It was not able to provide high repeatability of results, because of uncontrolled feeding capacity and refining consistency. The refining method with Valley refiner did not have a lot of variables and showed stable and repeatable results in energy saving. The results of experiments showed that efficient enzymes impregnation is probably the main target with enzymes application for energy saving. During the work the fiberized pulp showed high accessibility to enzymatic treatment and liquid penetration without special impregnating equipment. The reason was that fiberized pulp has larger wood surface area and thereby the contact area between the enzymatic solution and wood is also larger. Standard size chip and crushed chip treatment without special impregnator of enzymatic solution was evaluated as not efficient and did not show visible, repeatable results in energy consumption decrease. Thereby it was concluded that using of fiberized pulp and Valley refiner for measurements of enzymes' effectiveness in SEC decrease is more suitable than normal size chip and crushed chip with “Bauer” refiner. Endoglucanase with 5 kg/t dosage showed about 20% energy consumption decrease. Mixture of enzymes with 1.5 kg/t dosage showed about 15% decrease of energy consumption during the refining. Pectinase at different dosages and treatment times did not show significant effect on energy consumption. Results of knowledge discovery in databases showed the xylanase, cellulase and pectinase blend as most promising for energy reduction in TMP process. Surfactants were determined as effective additives for energy saving with enzymes.

Net melon resistance to Didymella bryoniae according to grafting and potassium levels

Chemical control of the fungus Didymella bryoniae, the causal agent of the disease gummy stem blight in melon, is frequently inefficient; thus, alternatives such as grafting and nutrition must be studied. Rootstocks and potassium levels were tested aimed at controlling this disease in net melon under protected environment. The melon hybrid 'Bônus II', ungrafted and grafted onto 'Dinero' melon and 'Strong Tosa' pumpkin rootstocks, was cultivated and inoculated by using the toothpick insertion method with 7-mm mycelial disks from the isolate D. bryoniae Dbr 37; for control, only toothpick insertion was used. The plants were subjected to the following potassium levels: 0, 62.5, 125, 187.5, 250 mg L-1. Grafted 'Bônus II' melon plants were resistant to the fungus, whereas ungrafted ones were susceptible. The adopted potassium levels did not influence the stem lesion size or the survival of plants.

Episodes in carbohydrate chemistry : from β-linked mannosides to glycoconjugates

Carbohydrates are one of the most abundant classes of biomolecules on earth. In the initial stages of research on carbohydrates much effort was focused on investigation and determination of the structural aspects and complex nature of individual monosaccharides. Later on, development of protective group strategies and methods for oligosaccharide synthesis became the main topics of research. Today, the methodologies developed early on are being utilized in the production of carbohydrates for biological screening events. This multidisciplinary approach has generated the new discipline of glycobiology which focuses on research related to the appearance and biological significance of carbohydrates. In more detail, studies in glycobiology have revealed the essential roles of carbohydrates in cell-cell interactions, biological recognition events, protein folding, cell growth and tumor cell metastasis. As a result of these studies, carbohydrate derived diagnostic and therapeutic agents are likely to be of growing interest in the future. In this doctoral thesis, a journey through the fundamentals of carbohydrate synthesis is presented. The research conducted on this journey was neither limited to the study of any particular phenomena nor to the addressing of a single synthetic challenge. Instead, the focus was deliberately shifted from time to time in order to broaden the scope of the thesis, to continue the learning process and to explore new areas of carbohydrate research. Throughout the work, several previously reported synthetic protocols, especially procedures related to glycosylation reactions and protective group manipulations, were evaluated, modified and utilized or rejected. The synthetic molecules targeted within this thesis were either required for biological evaluations or utilized to study phenomena occuring in larger molecules. In addition, much effort was invested in the complete structural characterization of the synthesized compounds by a combination of NMR spectroscopic techniques and spectral simulations with the PERCH-software. This thesis provides the basics of working with carbohydrate chemistry. In more detail, synthetic strategies and experimental procedures for many different reactions and guidelines for the NMR-spectroscopic characterization of oligosaccharides and glycoconjugates are provided. Therefore, the thesis should prove valuable to researchers starting their own journeys in the ever expanding field of carbohydrate chemistry.