Estudo do comportamento fotocrómico de um naftopirano: uma experiência simples ilustrativa do fotocromismo

An easy experiment on the synthesis of 3,3-diphenyl-3H-naphtho[2,1-b]pyran and characterization of its photochromic behaviour is reported. Upon irradiation of an uncoloured toluene solution of 3,3-diphenyl-3H-naphtho[2,1-b]pyran with near UV light, an intense yellow colouration is produced due to the formation of two coloured open forms. When the irradiation source is removed the coloured open forms return to the uncoloured state. The analysis of the absorbance decay with time allows the determination of the discoloration rate constants of each open form. The reversibility of the photochromic phenomenon, well demonstrated by the exposure of the solution to sunlight for a few seconds, is particularly attractive to the students.

Factors affecting the usability of aspen (Populus tremula) wood dried at different temperature levels

In this dissertation the main aim was to study the usability of aspen wood in the mechanical wood processes, especially the factors that affect the usability of aspen wood, which is dried at different temperature levels. The problematic of varying temperatures from level to another seem to have significant effects on distortions. According to the studies conducted, many practical solutions for drying of aspen timber can be made. European aspen sawn timber should be dried in relatively narrow widths, short lengths, edged and sawn pith free. The results achieved give an interesting view for the distortions of aspen wood between HT drying and heat treatment. The most significant result is that cupping seems to decrease when increasing temperature level from HT drying to heat treatment phase. The difference is significant. Other very obvious result is that bow and crook are increasing between these two temperature levels, bow significantly. Also the modelling gives a good background for this result since cupping is reduced by higher temperatures. It can also be assumed that these distortions can be affected for example by sorting out the timber used to different moisture levels before drying. This could be a very simple solution for practical purposes. From practical point of view, it was also noted during the drying tests performed that the discoloration seem to be no problem for aspen boards dried in temperatures under 150 °C. Altogether, this dissertation covers many interesting points of view of factors affecting distortions of wood in different temperature stages. Aspen as species in use of mechanical wood industries seems to be a species suitable for component production. According to the results, the best yield from aspen timber can be achieved in industry that can utilize relatively short components of sawn wood. Results achieved give a significant indication about the factors affecting distortions of wood at different temperature stages of drying, especially considering European aspen.

Degradação fotoeletroquímica de corantes dispersos em efluente têxtil utilizando fotoanodos de Ti/TiO2

The degradation of disperses dyes in aqueous solution and in effluents from textile industry has been investigated by photoelectrocatalytic oxidation using nanoporous thin films electrodes of Ti/TiO2. Samples of dispersil black dye and dispersil blue dye after 300 min of photoelectrolyzed at applied potential of +1.0 V and UV irradiation exhibited 100% of discoloration and 90% and 64% reduction total organic carbon, respectively. The proposed method was applied with success in a textile industry effluent containing residues of these dyes, which after 300 min of treatment leads to reduction of 60% of COD and 64% removal of TOC.

Nióbia sintética modificada como catalisador na oxidação de corante orgânico: utilização de H2O2 e O2 atmosférico como oxidantes

In this work synthetic niobia was used to promote the oxidation of methylene blue dye in aqueous medium. The niobia was characterized by N2 adsorption/desorption, XRD and TG measurements. The presence of reactive species on the niobia surface strongly increased the oxidation rate of the methylene blue dye. The reaction mechanism was studied by ESI-MS suggesting that the oxidation of the organic dye involve oxidizing species generated mainly after previous treatment with H2O2. It can be observed that the catalyst is a good material in the activation of gas (atmospheric oxygen) or liquid (hydrogen peroxide) oxidant agent with a total discoloration of the dye solution after only 1 h of reaction.

Descoloração e degradação do azo corante Vermelho GRLX-220 por ozonização

The discoloration and degradation of the textile dye RED GRLX-220 using the electrochemically generated ozone was investigated. Total discoloration was rapidly achieved in both acid and basic conditions. A pseudo-first order kinetics was observed for discoloration, influenced by pH and ozonation time. A considerable degree of mineralization (60%) was obtained after 30 min of ozonation in alkaline medium. The feasibility of organic matter oxidation during the ozonation process increased in both acidic and alkaline media. The toxicity decreased after the ozonation process, suggesting that the byproducts are less toxic than the parental compound.

Vanadato de bismuto sintetizado por combustão em solução na presença de diferentes combustíveis: síntese, caracterização e estudo da atividade fotocatalítica

In this manuscript, a BiVO4 semiconductor was synthesized by solution combustion synthesis using different fuels (Alanine, Glycine and Urea). Also, the Tween® 80 surfactant was added during synthesis. BiVO4 was characterized by XRD, SEM and diffuse reflectance spectroscopy. Photocatalytic activity was evaluated by the discoloration of methylene blue at 664 nm under UV-visible light irradiation. According to XRD, the monoclinic phase of BiVO4 was obtained for the samples. The smallest particle size and highest k obs value were observed for the BiVO4/alanine sample, which promoted greater demethylation of methylene blue.

In vitro toxin production by Fusarium solani f. sp. piperis

Fusarium solani f. sp. piperis (teleomorph: Nectria haematococca f. sp. piperis), causal agent of root rot and stem blight on black pepper (Piper nigrum), produces secondary metabolites with toxigenic properties, capable of inducing vein discoloration in detached leaves and wilting in transpiring microcuttings. Production of F. solani f. sp. piperis (Fsp) toxic metabolites reached a peak after 25 days of static incubation on potato sucrose broth at 25 ºC under illumination. Changes in the pH of the culture filtrate did not alter the effect of toxic metabolites. However, when the pH was changed before the medium had been autoclaved, a more intense biological response was observed, with an optimum at pH 6.0. Isolates that produced red pigments in liquid cultures were more efficient in producing biologically active culture filtrates than those which produced pink coloured or clear filtrates suggesting that these pigments could be related to toxigenic activity. Detached leaves of seven black pepper cultivars and Piper betle showed symptoms of vein discoloration after immersion in autoclaved and non-autoclaved Fsp culture filtrates indicating the thermostable nature of these toxic metabolites.

Pathogenicity evaluation of Cytospora eucalypticola isolated from Eucalyptus spp: cankers in Uruguay

Cytospora eucalypticola has been frequently associated with twig and stem cankers and as endophyte of Eucalyptus globulus and E. grandis in Uruguay. Mycelium discs of two C. eucalypticola isolates obtained from actively growing colonies were inoculated, both superficially and on experimentally wounded stems of E. globulus and E. grandis. No inoculated and control plants have shown any discoloration, gumosis or necrosis nor did they display lesions ten months after inoculation. Callus tissue was formed, partially or wholly occluding the wounds. The ability to penetrate healthy tissues and the inability to produce lesions evidenced that the presence of C. eucalypticola in twig and stem cankers could result from saprotrophic expansion of the endophytic mycelium in dying tissues, cankers probably being produced by different environmental stress conditions.

Ultrastructural observation of the airways of recovered and susceptible pigs after inoculation with Mycoplasma hyopneumoniae

To determine the morphological differences in the epithelium of the airways of recovered and susceptible pigs after Mycoplasma hyopneumoniae challenge, twenty-four 4-week-old M. hyopneumoniae-free pigs were intratracheally inoculated with 107ccu/ml of a pure low-passaged culture of the P5722-3 strain of M. hyopneumoniae challenge material. Eight pigs (group I) were challenged at the beginning of the experiment and rechallenged 3 months later. Group II pigs were also challenged at the beginning of the experiment and necropsied 3 months later. Group III pigs were challenged at the same time as the rechallenge of group I pigs. Eight nonchallenged pigs served as controls (group IV). Three days after the second challenge of group I and the first challenge of group III, and every 3 and 4 days thereafter, two pigs from each group were euthanatized by electrocution and necropsied. Samples of bronchi and lung tissue were examined using light and electron microscopy (SEM and TEM). Macroscopic lesions were observed in the lungs of all group III pigs (average = 4.74%) and were characterized by purple-red areas of discoloration and increased firmness affecting the cranioventral aspect of the lungs. Macroscopic lesions of pneumonia in groups I and II were minimal (less than 1%). There were no gross lesions of pneumonia in control (group IV) pigs. Microscopic lesions were characterized by hyperplasia of the peribronchial lymphoid tissue and mild neutrophilic infiltrates in alveoli. Electron microscopy showed patchy areas with loss of cilia and presence of leukocytes and mycoplasmas in bronchi of susceptible pigs (group III). The bronchial epithelium of rechallenged (group I), recovered (group II), and control (group IV) pigs was ultrastructurally similar indicating recovery of the former two groups. Although mycoplasmas were seen among cilia, a second challenge on pigs of group I did not produce another episode of the disease nor did it enhance morphological changes, suggesting that those pigs could become carriers of M. hyopneumoniae.

Experimental intoxication by the leaves of Melia azedarach (Meliaceae) in cattle

Green leaves of Melia azedarach were administered at single doses ranging from 5 to 30 g/kg bw to 11 calves. Clinical signs were depression, ruminal stasis, dry feces with blood, ataxia, muscle tremors, sternal recumbency, hypothermia and abdominal pain. Serum AST and CPK were increased. Signs appeared from 8 to 24 hours after dosing, and the clinical course lasted from 2 to 72 hours. Three calves dosed with 30g/kg bw died. The macroscopic findings included intestinal congestion, yellow discoloration of the liver, brain congestion and dry feces with blood in the rectum. The liver showed swollen and vacuolated hepatocytes. Necrotic hepatocytes were scattered throughout the parenchyma or concentrated in the periacinar zone. Degenerative and necrotic changes were observed in the epithelium of the forestomachs. There was also necrosis of the lymphoid tissue. Skeletal muscles showed hyaline degeneration and fiber necrosis. The necrotic fragments contained floccular or granular debris with infiltration by macrophages and satellite cells.

Equine leukoencephalomalacia (ELEM) due to fumonisins B1 and B2 in Argentina

In August 2007 an outbreak of neurological disease and sudden death in Arabian horses occurred in a farm located in Coronel Rosales County, Buenos Aires Province, Argentina. The animals were on a pasture of native grasses and supplemented ad libitum with corn kernels and wheat bran. Three horses were observed having acute neurologic signs including blindness, four leg ataxia, hyperexcitability, aimless walking and circling, followed by death in two of them. Four other horses were found dead overnight without a history of neurologic signs. The morbidity, mortality and lethality rates were 11.6%, 10% and 85.7%, respectively. Grossly, the brain showed focal areas of hemorrhage, brown-yellow discoloration and softening of the sub-cortical white matter. The microscopic brain lesions consisted of extensive areas of malacia within the white matter of the cerebral hemispheres, brainstem and cerebellum, characterized by rarefaction of the white matter with cavitations filled with proteinaceous edema, multifocal hemorrhages and mild infiltration by neutrophils, and rare eosinophils. Swollen glial cells with abundant eosinophilic cytoplasm, distinct cell borders, intracytoplasmic deeply eosinophilic globules and eccentric, hyperchromatic, occasionally pyknotic nucleus were present throughout the areas of rarefaction hemorrhage, edema and necrosis. The feed supplements contained 12,490µg/kg of fumonisin B1 and 5,251µg/ kg of fumonisin B2. This is the first reported outbreak of ELEM associated with consumption of feed supplements containing high concentrations of fumonisins in Argentina.

Ultraviolet light protection and weathering properties of wood-polypropylene composites

The main aim of this thesis is to study the effect of pigments on the weathering properties of wood-polypropylene composites (WPC). The studied properties are color change, water absorption, thickness swelling and Charpy impact strength. The impact of weathering and UV exposure on WPCs was studied by using pigments and minerals as protective agents. The study shows that the pigments and/or mineral fillers can be used to improve the weathering properties of WPCs. The effect of pigments was found to vary with the type of pigment and the method of weathering. The black pigment, an inorganic carbon black master-batch, was found to be the most effective one in reduction of the discoloration of WPCs. By preventing discoloration, and further reducing the degradation of the surface of the WPC, the pigments were found to reduce the decrease in the impact strength after weathering. As well as UV protection, the moisture resistance is a significant factor affecting the durability of WPCs. The addition of mineral fillers was found to improve the moisture-related properties, such as water absorption and thickness swelling, of WPC significantly. According to the findings, addition of pigments and mineral fillers to wood-polypropylene composites appears to be beneficial: color stability and moisture resistance can be enhanced especially in outdoor weathering. The combined effect of black pigment (carbon black master-batch) and wollastonite as a mineral filler was found to bring about the most effective properties against weathering.

Characterization of fruits from the savanna: Araça (Psidium guinnensis Sw.) and Marolo (Annona crassiflora Mart.)

The objective of this work was to characterize fruits from the Brazilian savanna by means of physical and chemical analyses. The results obtained for araça peel, araça pulp and marolo pulp, respectively, were: moisture (77.03, 80.41 and 70.56 g.100 g-1), ash (0.65, 0.44 and 0.54 g.100 g-1), protein (1.39, 1.87 and 1.99 g.100 g-1), lipids (0.32, 0.33 and 2.36 g.100 g-1), total carbohydrates (90.88 , 78.25 and 24.55 g.100 g-1), total soluble sugars (8.45, 9.99 and 127.4 g.100 g-1), pH (3.76, 3.99 and 4.49), soluble solids (11° Brix, 8.8 °Brix and 21.4 °Brix) and antioxidant potential (16.33, 12.75 and 34.29 discoloration DPPH/100 mL). Calcium was the predominant mineral in araça (490 mg.kg-1 peel and 485 mg.kg-1 pulp) while magnesium was in marolo (350 mg.kg-1). Citric acid was the predominant organic acid in araça (3125 μg.g-1 peel and 881.25 μg.g-1 pulp) and Malic acid was predominant in marolo (76.68 μg.g-1). Therefore, given their nutrient contents, the consumption of these fruits from the savanna should be encouraged.

Stability of frozen marolo pulp during storage

Marolo, also known as araticum or head-to-black, is a globular berry, a species native to the Brazilian savannah. The aim of this study was to evaluate the physical, chemical, and microbiological stability of frozen marolo pulp during 12 months of frozen storage. It was observed that the levels of ash (0.28-0.22%), protein (0.77-0.71%), lipids (1.75-1.73%), carbohydrates (12.1-10.15%), calorie (67.23-59.01 kcal), sucrose (2.50-1.29%), citric acid (435.63-197.5 µg.g-1), tartaric acid (4.38-1.88 µg.g-1) , acetic acid (470.38-279.25 µg.g-1), ascorbic acid (3.00-0.00 µg.g-1), total pectin (0.67-0.39%), pH (3.88-3.83), and b* chromaticity coordinates (24.85-20.53) decreased reduced during storage, whereas the levels of moisture (85.10-87.19%), color parameters (L* 58.89-62.62 and a* 5.37-7.86), reducing sugars (4.53-5.62%), total soluble sugars (7.1-7.36%), soluble solids (7.0-8.4 ºBrix), total acidity (0.9-1.0%), malic acid (514.13-781.25 µg.g-1), soluble pectin (0.16-0.24%), and antioxidant (6.85-37.35% of DPPH discoloration) increased over the one-year of storage period. According to the physical, chemical, and microbiological parameters assessed, the product can be stored for 12 months without loss of quality with addition of citric acid as a preservative.

Caracterització i revaloració de la fracció plasmàtica de la sang de porc procedent d'escorxadors industrials

La tesi s'ha estructurat en tres apartats que, en conjunt, han de permetre determinar les possibilitats d'aprofitament dins la mateixa indústria alimentària de la fracció plasmàtica de la sang de porc generada per escorxadors que utilitzen sistemes oberts de recollida higiènica. 1. En la primera part s'analitza la composició de la sang higiènica que s'està recollint actualment i s'estudien les característiques tant físico-químiques com microbiològiques que determinen la seva qualitat. La caracterització s'ha realitzat amb sang recollida en diferents escorxadors industrials de les comarques de Girona i s'ha centrat principalment en l'estudi de la contaminació microbiològica i el nivell d'hemòlisi de la sang. S'ha fet un disseny experimental que ha permès alhora valorar l'efecte d'alguns factors sobre la qualitat de la sang: possibles diferències relacionades amb (1) la climatologia del període de l'any en el qual es fa la recollida, (2) particularitats dels escorxadors (grandària, sistemes de dessagnat, tipus, dosi i sistema de dosificació de l'anticoagulant, condicions de processament, maneig i emmagatzematge després de la recollida, etc.). Els resultats obtinguts ens permeten constatar que, en les condicions actuals, la sang que s'està recollint en els escorxadors estudiats no es pot considerar adequada per a una matèria primera de productes destinats a alimentació humana. La major part de la microbiota contaminant s'adquireix en el propi sagnador. S'ha constatat que el sistema de dessagnat en posició horitzontal podria ser una mesura útil per minimitzar la contaminació d'origen fecal o provinent de la pell de l'animal sacrificat i que la separació immediata de les fraccions en el propi escorxador també pot contribuir a reduir la contaminació. Així doncs, en el benentès que l'efectivitat pot obtenir-se del conjunt de mesures preses, més que de l'aplicació d'una sola d'elles, es suggereix la introducció d'una sèrie d'actuacions que potser permetrien reduir els nivells de contaminació que s'obtenen actualment. El tractament mecànic de la sang, el sistema d'addició d'anticoagulant, el volum i concentració de la solució anticoagulant afegida i el període d'emmagatzematge són els factors responsables de l'hemòlisi; mentre que nivells elevats de contaminació microbiològica i el tipus d'anticoagulant utilitzat deterrminen la velocitat d'increment de l'hemòlisi de sang refrigerada. S'ha constatat que quan la sang no pot ser processada immediatament i s'ha d'emmagatzemar en refrigeració és millor utilitzar citrat sòdic enlloc de polifosfat com a anticoagulant ja que l'increment d'hemòlisi es dóna més lentament. 2. El segon apartat s'ha centrat en la fracció plasmàtica de la sang. S'ha utilitzat la deshidratació per atomització com a tecnologia de conservació del plasma i s'ha fet una caracterització del producte en pols resultant des del punt de vista de composició i qualitat. A més de la contaminació microbiològica, que determina la qualitat higiènico-sanitària del producte, s'ha realitzat un estudi de les propietats funcionals que podrien fer del plasma un producte útil en la formulació d'aliments (capacitat escumant, emulsionant, gelificant). S'ha fet especial incidència en (1) determinar l'efecte del procés tecnològic de deshidratació sobre la funcionalitat del producte i (2) estudiar l'estabilitat del plasma deshidratat durant el període d'emmagatzematge. En les condicions de deshidratació per atomització aplicades no es provoca desnaturalització de la fracció proteica i s'obté un producte suficientment deshidratat, amb una aw<0,4 per permetre suposar una bona estabilitat. Algunes mostres de plasma deshidratat analitzades presenten nivells detectables de determinats residus (sulfonamides i corticosteroides). La qualitat microbiològica del producte en pols reflecteix l'elevada contaminació que contenia la matèria primera utilitzada, tot i que la deshidratació per atomització ha comportat la reducció en una unitat logarítmica de la càrrega contaminant. Els recomptes generals de microorganismes són encara preocupants i més tenint en compte que s'ha evidenciat la presència de toxines estafilocòciques en algunes mostres. L'avaluació de les propietats funcionals del producte deshidratat en relació a les que presentava el plasma líquid ens ha permès comprovar que: (1) El procés de deshidratació no ha afectat la solubilitat de les proteïnes. Això, junt amb el fet que no s'obtinguin diferències significatives en l'anàlisi calorimètrica de mostres líquides o deshidratades, permet concloure que el procés no provoca desnaturalització proteica. (2) No s'observen efectes negatius del procés tecnològic sobre la capacitat escumant ni en l'activitat emulsionant de les proteïnes plasmàtiques, dues propietats funcionals que possibiliten l'aplicació del plasma amb aquestes finalitats en l'elaboració d'alguns aliments. (3) La deshidratació tampoc perjudica de manera important les característiques dels gels que s'obtenen per escalfament, ja que els gels obtinguts a partir del plasma líquid i del plasma deshidratat presenten la mateixa capacitat de retenció d'aigua i no s'observen diferències en la microestructura de la xarxa proteica d'ambdós tipus de gel. Tanmateix, els que s'obtenen a partir del producte en pols mostren una menor resistència a la penetració. L'estudi d'estabilitat ens ha permès comprovar que la mostra de plasma deshidratat per atomització perd algunes de les seves propietats funcionals (facilitat de rehidratació, capacitat de retenció d'aigua i fermesa dels gels) si s'emmagatzema a temperatura ambient, mentre que aquestes característiques es mantenen un mínim de sis mesos quan el producte en pols es conserva a temperatura de refrigeració. 3. En l'última part, tenint en compte les conclusions derivades dels resultats dels apartats anteriors, s'han assajat tres possibles sistemes de reducció de la contaminació aplicables a la fracció plasmàtica com a pas previ a la deshidratació, per tal de millorar les característiques de qualitat microbiològica i les perspectives d'estabilitat del producte durant l'emmagatzematge. S'ha determinat l'eficàcia, i l'efecte sobre les propietats del plasma deshidratat, que poden tenir tractaments d'higienització basats en la centrifugació, la microfiltració tangencial i l'aplicació d'altes pressions. Els tractaments de bactofugació aplicats permeten reduir entre el 96 i el 98% la contaminació microbiana del plasma. Aquesta reducció s'aconsegueix tant amb un sistema discontinu com amb un sistema continu treballant a una velocitat de 12 L/h, fet que permetria adaptar el tractament de bactofugació a un procés de producció industrial. Un sistema combinat de bactofugació en continu i microfiltració tangencial permet incrementar l'eficàcia fins a un 99,9 % de reducció. Cal tenir present, però, que aquest tractament provoca també una disminució de l'extracte sec que afecta negativament les propietats funcionals del plasma líquid. Malgrat suposar una pèrdua pel que fa al rendiment, aquest efecte negatiu sobre la funcionalitat no suposaria cap inconvenient si s'utilitzés la deshidratació com a tecnologia de conservació del plasma, ja que es podria corregir l'extracte sec durant la reconstitució del producte. Caldria avaluar si la millora en la qualitat higiènico-sanitària del producte compensa o no les pèrdues que suposa aquest sistema d'higienització combinat. Amb relació als tractaments d'alta pressió, de totes les condicions de tractament assajades, les pressions de fins 450 MPa permeten obtenir plasma sense modificacions importants que impedeixin la seva deshidratació per atomització. Així doncs, les condicions de procés que s'han aplicat són pressuritzacions a 450 MPa de 15 minuts de durada. La temperatura de tractament que s'ha mostrat més eficaç en la reducció dels recomptes de microorganismes ha estat de 40ºC. Els tractaments a aquesta temperatura permeten assolir reduccions del 99,97% i disminuir en un 80% la capacitat de creixement dels microorganismes supervivents a la pressurització en relació a la que presentava la població contaminant del plasma abans del tractament. L'estudi de l'efecte d'aquest tractament (450 MPa, 15 min i 40ºC) sobre les propietats funcionals del plasma ha permès observar que la pressurització comporta una disminució en la solubilitat del producte però una millora en les propietats de superfície -estabilitat de l'escuma i activitat emulsionant- i un increment de la capacitat de retenció d'aigua i de la duresa dels gels obtinguts per escalfament. Calen més estudis per confirmar i caracteritzar aquesta millora en la funcionalitat, així com per establir si el tractament de pressurització afecta també l'estabilitat del producte durant l'emmagatzematge. De totes les tecnologies d'higienització assajades, l'alta pressió és la que permet obtenir millors resultats en el sentit de poder garantir un producte de bona qualitat microbiològica i segur, des del punt de vista sanitari i tecnològic, per a la seva utilització com a ingredient alimentari.