Time-dependent DNA condensation induced by amyloid beta-peptide

The major protein component of the amyloid deposition in Alzheimer's disease is a 39-43 residue peptide, amyloid beta (A beta). A beta is toxic to neurons, although the mechanism of neurodegeneration is uncertain. Evidence exists for non-B DNA conformation in the hippocampus of Alzheimer's disease brains, and A beta was reportedly able to transform DNA conformation in vitro. In this study, we found that DNA conformation was altered in the presence of A beta, and A beta induced DNA condensation in a time-dependent manner. Furthermore, A beta sheets, serving as condensation nuclei, were crucial for DNA condensation, and Cu2+ and Zn2+ ions inhibited A beta sheet-induced DNA condensation. Our results suggest DNA condensation as a mechanism of A beta toxicity.

Physical and spectral characterization of the human cyclin A gene and its interactions with anthracycline anticancer drugs

Over expression of cyclin A in human tumors has been linked to cancer by various experimental lines of evidence. However, physical and spectral characterization of the human cyclin A gene and its interactions with anticancer drugs have not been reported. Our gene sequence analysis, singular value decomposition method and melting studies in the presence of antitumor agents, daunomycin, doxorubicin and Hoechst 33258 showed that cyclin A gene had both AT-rich and GC-rich domains. For a ligand with unknown DNA binding specificity, this gene sequence can be used to differentiate its DNA binding preference.

Construction of a heteropolyanion-modified electrode by a two-step sol-gel method and its electro catalytic applications

The sol-gel technique was used here to construct heteropolyanion-containing modified electrodes. This involves two steps, i.e. the first forming a functionalized sol-gel thin film on the surface of the glassy carbon electrode and then immersing the electrode into a heteropolyanion solution to incorporate the heteropolyanion into the sol-gel film. Here a Dawson-type heteropolyanion, K6P2W18O62 (P2W18), was used as a representative to illuminate the behavior of the as-prepared composite film. The electrochemical performance of the P2W18-modified electrode was studied with respect to the pH effect and long-term stability. The modified electrode exhibited a high electrocatalytic response for the reduction of BrO3- and NO2-. Steady-state amperometry was applied to characterize the electrode as an amperometric sensor for the determination of NO2-. The sensor had a linear range from 0.02 to 34 mM and a detection limit of 5 x 10(-6) M. (C) 2001 Elsevier Science B.V. All rights reserved.

Recognition interactions of metal-complexing imprinted polymer

Molecularly imprinted polymer, exhibiting considerable enantioselectivity for L-mandelic acid, was prepared using metal coordination-chelation interaction. By evaluating the recognition characteristics in the chromatographic mode, the recognition interactions were proposed: specific and nonspecific metal coordination-chelation interaction and hydrophobic interaction were responsible for substrate binding on metal-complexing imprinted polymer; while the selective recognition only came from specific metal coordination-chelation interaction and specific hydrophobic interaction.

Badania spektroskopowe, strukturalna i aktywność przeciwdrobnoustrojowa nowych soli kwasu lasalowego z aminami

Wydział Chemii

Engineering bio-based polymers using alternative solvents and processes

The work presented in this thesis explores novel routes for the processing of bio-based polymers, developing a sustainable approach based on the use of alternative solvents such as supercritical carbon dioxide (scCO2), ionic liquids (ILs) and deep eutectic solvents (DES). The feasibility to produce polymeric foams via supercritical fluid (SCF) foaming, combined with these solvents was assessed, in order to replace conventional foaming techniques that use toxic and harmful solvents. A polymer processing methodology is presented, based on SCF foaming and using scCO2 as a foaming agent. The SCF foaming of different starch based polymeric blends was performed, namely starch/poly(lactic acid) (SPLA) and starch/poly(ε-caprolactone) (SPCL). The foaming process is based on the fact that CO2 molecules can dissolve in the polymer, changing their mechanical properties and after suitable depressurization, are able to create a foamed (porous) material. In these polymer blends, CO2 presents limited solubility and in order to enhance the foaming effect, two different imidazolium based ILs (IBILs) were combined with this process, by doping the blends with IL. The use of ILs proved useful and improved the foaming effect in these starch-based polymer blends. Infrared spectroscopy (FTIR-ATR) proved the existence of interactions between the polymer blend SPLA and ILs, which in turn diminish the forces that hold the polymeric structure. This is directly related with the ability of ILs to dissolve more CO2. This is also clear from the sorption experiments results, where the obtained apparent sorption coefficients in presence of IL are higher compared to the ones of the blend SPLA without IL. The doping of SPCL with ILs was also performed. The foaming of the blend was achieved and resulted in porous materials with conductivity values close to the ones of pure ILs. This can open doors to applications as self-supported conductive materials. A different type of solvents were also used in the previously presented processing method. If different applications of the bio-based polymers are envisaged, replacing ILs must be considered, especially due to the poor sustainability of some ILs and the fact that there is not a well-established toxicity profile. In this work natural DES – NADES – were the solvents of choice. They present some advantages relatively to ILs since they are easy to produce, cheaper, biodegradable and often biocompatible, mainly due to the fact that they are composed of primary metabolites such as sugars, carboxylic acids and amino-acids. NADES were prepared and their physicochemical properties were assessed, namely the thermal behavior, conductivity, density, viscosity and polarity. With this study, it became clear that these properties can vary with the composition of NADES, as well as with their initial water content. The use of NADES in the SCF foaming of SPCL, acting as foaming agent, was also performed and proved successful. The SPCL structure obtained after SCF foaming presented enhanced characteristics (such as porosity) when compared with the ones obtained using ILs as foaming enhancers. DES constituted by therapeutic compounds (THEDES) were also prepared. The combination of choline chloride-mandelic acid, and menthol-ibuprofen, resulted in THEDES with thermal behavior very distinct from the one of their components. The foaming of SPCL with THEDES was successful, and the impregnation of THEDES in SPCL matrices via SCF foaming was successful, and a controlled release system was obtained in the case of menthol-ibuprofen THEDES.

Évaluation et modélisation de l’impact de la coexposition de composés organiques volatils sur l’excrétion de leurs biomarqueurs urinaires

L’évaluation de l’exposition aux composés organiques volatils (COV) recourt couramment à l’analyse des métabolites urinaires en assumant qu’aucune interaction ne survient entre les composés. Or, des études antérieures ont démontré qu’une inhibition de type compétitive survient entre le toluène (TOL), l’éthylbenzène (EBZ) et le m-xylène (XYL). Le chloroforme, qui est également un solvant métabolisé par le CYP2E1, se retrouve souvent en présence des autres COV dans les échantillons de biosurveillance. La présente étude visait donc à évaluer si le chloroforme (CHL) peut lui aussi interagir avec ces COV et évaluer ces interactions au niveau de l’excrétion des biomarqueurs urinaires associés, soit l’o-crésol, l’acide mandélique et l’acide m-méthylhippurique pour TOL, EBZ et XYL respectivement. Afin d’obtenir des données humaines, cinq volontaires ont été exposés par inhalation à différentes combinaisons de COV (seuls et mélanges binaires ou quaternaires) où la concentration de chacun des composés était égale à 1/4 ou 1/8 de la valeur limite d’exposition (VLE) pour une durée de 6h. Des échantillons d’air exhalé, de sang et d’urine ont été récoltés. Ces données ont ensuite été comparées aux modèles pharmacocinétiques à base physiologique (PCBP) existants afin de les ajuster pour l’excrétion urinaire. Certaines différences ont été observées entre les expositions aux solvants seuls et les coexpositions, mais celles-ci semblent majoritairement attribuables aux remplacements de participants à travers les différentes expositions. Les valeurs de Vmax pour EBZ et CHL ont été optimisées afin de mieux prédire les niveaux sanguins de ces COV. À l’exception du modèle pour EBZ, tous les paramètres pour l’excrétion urinaire ont été obtenus à partir de la littérature. Les modèles adaptés dans cette étude ont permis de simuler adéquatement les données expérimentales.

Protein-lipid interactions at the air/water interface

Surface pressure measurements and external reflection FTIR spectroscopy have been used to probe protein-lipid interactions at the air/water interface. Spread monomolecular layers of stearic acid and phosphocholine were prepared and held at different compressed phase states prior to the introduction of protein to the buffered subphase. Contrasting interfacial behaviour of the proteins, albumin and lysozyme, was observed and revealed the role of both electrostatic and hydrophobic interactions in protein adsorption. The rate of adsorption of lysozyme to the air/water interface increased dramatically in the presence of stearic acid, due to strong electrostatic interactions between the negatively charged stearic acid head group and lysozyme, whose net charge at pH 7 is positive. Introduction of albumin to the subphase resulted in solubilisation of the stearic acid via the formation of an albumin-stearic acid complex and subsequent adsorption of albumin. This observation held for both human and bovine serum albumin. Protein adsorption to a PC layer held at low surface pressure revealed adsorption rates similar to adsorption to the bare air/water interface and suggested very little interaction between the protein and the lipid. For PC layers in their compressed phase state some adsorption of protein occurred after long adsorption times. Structural changes of both lysozyme and albumin were observed during adsorption, but these were dramatically reduced in the presence of a lipid layer compared to that of adsorption to the pure air/water interface.

The effect of proteolysis on the induction of cell death by monomeric alpha-lactalbumin.

α-Lactalbumin (α-la) is a major whey protein found in milk. Previous data suggested that α-la has antiproliferative effects in human adenocarcinoma cell lines such as Caco-2 and HT-29. However, the cell death inducing α-la was not a naturally occurring monomer but either a multimeric variant or an α-la:oleic acid complex (HAMLET/BAMLET). Proteolysis showed that both human and bovine α-la are susceptible to digestion. ELISA assays assessing cell death with the native undigested α-la fractions showed that undigested protein fractions did have a significant cell death effect on CaCo-2 cells. Bovine α-la was also more effective than human α-la. A reduction in activity corresponded with lower concentrations of the protein and partial digestion and fragmentation of the protein using trypsin and pepsin. This suggests that the tertiary structure is vital for the apoptotic effect.

Europium luminescent polymeric microspheres fabricated by spray drying process

The spray drying method was used to prepare luminescent microspheres. These microspheres were prepared by spraying an aqueous solution of dextrin and an europium(III) complex with subsequent drying in a hot medium. The spray dried powder was characterized by scanning electron microscopy (SEM) and photoluminescence spectroscopy (PL). Particle size distribution was estimated from SEM images. The ultrasonic spray drying technique was successfully applied to yield a microparticulated and red luminescent powder composed by the [Eu(dpa)(3)](3-) stop (dpa = dipicolinic acid) complex incorporated in dextrin microspheres.

Relative bioavailability of zinc in supplemental inorganic and organic sources for Nile tilapia Oreochromis niloticus fingerlings

A 90-day feeding experiment was conducted with sex reversed Nile tilapia (Oreochromis niloticus) fingerlings fed purified or practical diets supplemented with different zinc sources to evaluate fish growth performance and zinc and iron retention in fish bones, fillets, liver, skin and eyes. The relative bioavailability value (RBV) of zinc in the supplemental sources tested was also calculated. Fish were fed with isonitrogenous and isoenergetic purified or practical diets supplemented with 150 mg Zn kg -1, as zinc sulphate monohydrate (ZnSO 4), zinc oxide (ZnO) or zinc amino acid complex (Zn-AA). The feeding trial was conducted in 30, 50 L aquaria where four 0.66 ± 0.01 g (mean ± SD) fingerlings were initially stocked. No significant differences were observed for any growth performance variables (P > 0.05). In practical diets, only ZnSO 4 and ZnO presented bone zinc retention similar to that for the standard zinc source. Zinc concentration in the bone of fish fed practical diet supplemented with Zn-AA (171 ± 3.62 μg g -1) was significantly lower than that verified for the practical diets supplemented with the standard zinc source (200 ± 17.7 μg g -1) or with ZnSO 4 (204 ± 19.9 μg g -1). Assuming the concentration of zinc in bones as the response criterion, the supplemental zinc RBV from ZnSO 4 (105%) was higher than the RBV for Zn-AA (95.1%) or ZnO (94.9%). Iron concentration in the bones of animals fed the non-zinc-supplemented purified diet was significantly higher than that observed for purified diet supplemented with Zn-AA (P < 0,05). The results of the present work allowed us to conclude that ZnSO 4 in relation to ZnO or Zn-AA was the supplemental zinc source with higher zinc bioavailability to Nile tilapia. © 2005 Blackwell Publishing Ltd.

Apparent absorption of zinc from supplemental inorganic and organic sources to Nile tilapia Oreochromis niloticus juveniles

Nile tilapia Oreochromis niloticus fingerlings were fed with purified or practical diets, supplemented with 150 Ing Zn/kg, from different sources. Dry matter (DM), crude protein (CP), ether extract (EE), and gross energy (GE) apparent digestibility coefficients (ADC), as well as zinc, copper, calcium, and phosphorus apparent absorption coefficients (AAC) were determined by the addition of 0.1% chromic oxide to the diets. The supplemental zinc sources utilized were commercial grade zinc sulfate monohydrate (ZnSO 4), zinc oxide (ZnO) and a zinc amino acid complex (Zn-AA). Analytical grade zinc sulfate heptahydrate was also utilized as a standard reference zinc source. There was a significant difference between purified (74.9%) and practical (41.3%) zinc AAC for the ZnO supplemented diets (P < 0.05). The supplemental zinc sources presented similar AAC when purified diets were utilized. However, ZnSO 4 was the best supplemental zinc source when practical type diets were used. There were no significant differences between supplemental zinc AAC from ZnS0 4 (68.9%), and supplemental zinc AAC from Zn-AA (61.3%) in practical diets, but Zn-AA diet showed a statistically lower zinc AAC when compared with the standard zinc source diet (75.6%). The practical diet supplemented with ZnO had the worst supplemental zinc AAC (41.3%). Dietary copper (74.21%), calcium (70.9%), and phosphorus (71.9%) AAC of the practical diets supplemented with ZnO were statistically lower (P < 0.05) than the respective AAC of the practical ZnSO 4 supplemented diets (83.6%, 84.1%, 87.1%).The ADC of the practical ZnO supplemented diet for DM (76.3%), CP (88.6%), EE (82.4%), and GE (81.6%) were statiscally lower than the respective ADC of the ZnSO 4 practical diet (86.0, 92.7, 93.6, 89.6%, respectively) and those ADC of the Zn-AA practical diet (84.7, 92.7, 93.7, 88.2%, respectively) (P < 0.05). Hence, these results indicate that ZnSO 4 and Zn-AA have equivalent intestinal absorption as supplemental zinc sources for Nile tilapia juveniles and both are superior to ZnO. © Copyright by the World Aquaculture Society 2005.

Alimentação de leitões com dietas contendo soro de leite fermentado mais zinco e cobre orgânico

An experiment was carried out to evaluate the performance of piglets fed rations containing fermented milk and zinc and copper amino acid complex. Sixty four piglets, littermates, were used. The experimental design was based on random block with two dietary treatments. One of these contained a basal diet (DB) with ZnO e CuSO 4 and the other one with the DB, but without CuSO 4 and with the addition of fermented milk and zinc and copper amino acid complex (SLF Lact +ZnCuAA). There were eight replicate pens per treatment, and pigs were grouped at 4 per pen. The SLF Lact + ZnCuAA didn't not affect (p>0.05) final live weight of the piglets. However, live weight was different (p<0.01) between males and females (24.3 vs. 24.0 kg) at end of experiment. The feed intake of animals feed with SLF Lact+ZnCuAA was higher (p<0.01) in 8% in the first 14 days (0.261 vs. 0.239 kg/d), 15% from 15 to 28 days (0.756 vs. 0.675 kg/ d) and 12% from 29 to 42 days (1.091 vs. 0.962 kg/ d) compared to control group. Daily average feed intake in the experimental period was 11% higher (p<0.01) for the animals fed with the diet contained SLF Lact+ZnCuAA. Weight gain of the treatment with SLFL act+ZnCuAA was higher (p<0.01) by 14% from 0 to 14 days (0.176 vs. 0.152 kg/d), 11% from 15 to 28 days (0.564 vs. 0.500 kg/d) and 12% from 29 to 42 days (0,572 vs. 0,501 kg/d). Average daily weight gain of 42 days of trial of treatment with SLF Lact +ZnCuAA was 12% higher (p<0.01) compared to control group (0.437 vs. 0.384 kg/d). Feed conversion ratio was 8% lower (p<0.01) for treatment with SLF Lact+ZnCuAA in the first 14 days (1.487 vs. 1.614). Supplementation with fermented milk and zinc and copper amino acid complex in diets containing zinc oxide improved growth performance of weanling piglets.

Síntese, caracterização e estudo termoanalítico dos mandelatos de alguns metais de transição bivalentes no estado sólido

Pós-graduação em Química - IQ

Estudo de comportamento térmico e de biodegradação de PHBV4% modificado com hidroxiácido

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)