Polymer Cocktail: A Multitask Supported Ionic Liquid‐Like Species to Facilitate Multiple and Consecutive C?C Coupling Reactions

Polymer‐supported ionic liquid‐like species (SILLPs) with different functionalities have been combined to obtain new catalytic systems (polymer cocktail) with improved properties towards their application for C C coupling reactions. The SILLPs have been synthesized in a simple way and combined to play different functions in the reaction medium. Those roles involve simultaneously (or consecutively) their actuation as supported reagents, precatalysts and scavengers of undesired reaction side‐products. The system has been tested by employing three different C C coupling reactions for 8 consecutive cycles. Moreover, different aryl bromides and iodides have proved to be efficiently transformed by the catalytic cocktail. Finally, the Heck reaction has been conducted in continuous‐flow conditions using a packed bed of this polymer cocktail and employing supercritical carbon dioxide (scCO₂) as a solvent, which cannot be carried out with the use of soluble bases as this would lead to the clogging of the reactor. Finally, the SILLPs cocktail enables one to combine different reaction steps and purification in a single vessel, which represents a significant improvement in terms of process intensification and green chemistry. This is particularly true in the case of the use of scCO₂ as this allows the direct production of crude materials not contaminated either by salts or by solvents.     

Gene Therapy in HIV‐Infected Cells to Decrease Viral Impact by Using an Alternative Delivery Method

The ability of dendrimer 2G‐[Si{O(CH₂)₂N(Me)₂⁺(CH₂)₂NMe₃⁺(I^?)₂}]₈ (NN16) to transfect a wide range of cell types, as well as the possible biomedical application in direct or indirect inhibition of HIV replication, was investigated. Cells implicated in HIV infection such as primary peripheral blood mononuclear cells (PBMC) and immortalized suspension cells (lymphocytes), primary macrophages and dendritic cells, and immortalized adherent cells (astrocytes and trophoblasts) were analyzed. Dendrimer toxicity was evaluated by mitochondrial activity, cell membrane rupture, release of lactate dehydrogenase, erythrocyte hemolysis, and the effect on global gene expression profiles using whole‐genome human microarrays. Cellular uptake of genetic material was determined using flow cytometry and confocal microscopy. Transfection efficiency and gene knockdown was investigated using dendrimer‐delivered antisense oligonucleotides and small interfering RNA (siRNA). Very little cytotoxicity was detected in a variety of cells relevant to HIV infection and erythrocytes after NN16 dendrimer treatment. Imaging of cellular uptake showed high transfection efficiency of genetic material in all cells tested. Interestingly, NN16 further enhanced the reduction of HIV protein 24 antigen release by antisense oligonucleotides due to improved transfection efficiency. Finally, the dendrimer complexed with siRNA exhibited therapeutic potential by specifically inhibiting cyclooxygenase‐2 gene expression in HIV‐infected nervous system cells. NN16 dendrimers demonstrated the ability to transfect genetic material into a vast array of cells relevant to HIV pathology, combining high efficacy with low toxicity. These results suggest that NN16 dendrimers have the potential to be used as a versatile non‐viral vector for gene therapy against HIV infection.     

Synthesis of Fatty Acid Amides of Catechol Metabolites that Exhibit Antiobesity Properties

A series of fatty acid amides of 3,4‐methylenedioxymethamphetamine (MDMA) catechol metabolites were synthesized in order to evaluate their biological activities. Upon administration, all synthesized compounds resulted in negative modulation of food intake in rats. The most active compounds have affinity for the CB₁ receptor and/or PPAR‐α; part of their biological activity may be caused by these double interactions.     

Ecological and biological determinants of trace elements accumulation in liver and kidney of Pontoporia blainvillei

The present work tested whether ecological and biological variables have an influence on the assimilation of trace elements by the tissues of a cetacean from the Western South Atlantic Ocean. No significant differences were observed in the concentrations for both sexes. As individuals from the two sampling areas belong to distinct genetic and morphological populations, animals of similar body length were older on the southeastern than on the southern coast. The liver showed the highest concentrations of mercury, whereas the highest levels of cadmium were found in the kidney. Hepatic mercury, cadmium and selenium in individuals from the south coast were about four times as high as those from the southeast coast. However, arsenic in the liver and kidney were similar in both coastal areas. Hepatic mercury, cadmium and selenium concentrations increased with body length in individuals from the southeastern coast, although no significant correlations (P>0.05) were observed between body length from either area and the renal and hepatic As concentrations. A significant positive linear relationship was observed between molar concentrations of Hg and Se in the liver of all individuals from both areas (r2=0.93; P<0.001), presenting Se:Hg ratios close to 4. Differences found among the concentrations of Hg, Cd and Se in dolphins from both areas were probably due to the preferred prey, bioavailability of elements in each marine environment, and environment variables (water temperature, net primary production). As a consequence, concentrations of trace elements in the tissues of this species can be considered to be a result of the surrounding environment.     

The association of dental caries with blood lead in children when adjusted for IQ and neurobehavioral performance

Associations between childhood lead exposures and dental caries in children have been reported for over 30 years, with widely varying findings and conclusions, and using measures of lead exposure which ranged from food sources and water to tooth, hair or blood lead concentrations. OBJECTIVES: This study examined the relationship of lead exposure and dental caries in a population of normatively healthy children. METHODS: This cross-sectional study used a population of 507 children aged 8-12 who were participating in a clinical trial of dental materials to examine the relationship between lead and caries. Blood lead concentrations and dental caries were examined for association in both primary and permanent teeth. Because it is possible that neurobehavioral status could be associated with both lead exposure and dental caries prevalence, we also examined neurobehavioral status of the subjects. RESULTS: A gender-specific association (males only) between lead exposure and dental caries was found in primary teeth only. Neurobehavioral measures and IQ were not associated with caries status in this population. CONCLUSIONS: This study did not support neurobehavioral status as mediating any association between lead exposure and caries in a normatively healthy population. A gender-specific association between lead and caries not previously reported was found in primary teeth, and no biological explanation for this has been suggested. We conclude that this study provides only weak evidence, if any, for an association of low-level lead exposure with dental caries.     

Decomposition of belowground litter and metal dynamics in salt marshes (Tagus Estuary, Portugal)

The concentrations of C, Fe, Mn, Zn, Cu, Pb and Cd were determined monthly in decomposing roots of Halimione portulacoides, using litterbag experiments, in two salt marshes of the Tagus estuary with different levels of contamination. Although carbon concentrations varied within a narrow interval during the experiment, litter decomposed rapidly in the first month (weight loss between 0.051 and 0.065 g d(-1)). The time variation of metals was examined in terms of Me/C ratios and metal stocks. Ratios of Fe/C and Mn/C and their metal stocks increased in spring, presumably due to the precipitation of oxides in the surface of decomposing roots. Subsequent decrease of Fe/C and Mn/C ratios suggests the use of Fe and Mn oxides, as electron acceptors, in the organic matter oxidation. Zinc, Cu, Pb and Cd ratios to C were, in general, higher than at initial conditions implying that metal that leached out was slower than carbon. However, metal stocks decreased during the experiment indicating that incorporation or sorption of metals in Fe and Mn oxides did not counterbalance the amount of Zn, Pb and Cd released from decomposing litter. An exception was observed for Cu, since stock in the less contaminated marsh (Pancas) increased during the decomposition, indicating that litter was efficient on Cu binding under more oxidising conditions. These results emphasize the importance of litter decomposition and sediment characteristics on metal cycling in salt marshes.     

Factors affecting the fate of active proteins introduced in wastewater sludges: investigation with green fluorescent protein

Green fluorescent protein (GFP) was used as a reporter protein to investigate the interactions and fate of the active conformation of proteins in wastewater sludge. GFP was chosen because its fluorescence is dependent on the integrity of its native conformation. We identified factors that cause the loss of GFP fluorescence when this protein is introduced in aerobic or anaerobic sludge. In both systems, soluble polymers present in the liquid fraction caused an initial loss of fluorescence, but stabilized the remaining fluorescent GFP molecules. In aerobic sludge, interaction of GFP with the sludge solids initially caused an additional loss of fluorescence but the remaining fluorescence kept fairly constant over the following hours. In anaerobic sludge, on the contrary, interaction of GFP with the sludge solids caused a temperature dependent loss of fluorescence, probably related to the presence of precipitated ferrous sulfide. No direct relationship was found between sludge protease activity and loss of GFP fluorescence, suggesting that proteases are not the primary factor controlling the fate of the active form of proteins in wastewater sludges.     

Lipolysis and lipid oxidation during chilled storage of meat from Large White and Pietrain pigs

The day after slaughter, six chops of Longissimus lumborum from each of 10 Large White pigs and six Piétrain pigs were packed individually under vacuum and kept at 3-4?°C in the dark. At 1, 5 and 9 days after slaughter, two chops were used for analysis of lipids, thiobarbituric acid reactive substances (TBARS), sarcoplasmic Ca(2+) and sarcoplasm and mitochondria phospholipase A(2) activity. Free fatty acid content was higher in Piétrains than in Large Whites and increased with keeping time. Total lipids of Large White pigs contained more saturated fatty acid (SFA) and monounsaturated fatty acid (MUFA) and less polyunsaturated fatty acid (PUFA). Large Whites had less dioleoyl-linoleyl-glycerol (OOL) and Palmitoyl-oleoyl-linoleyl-glycerol (POL) and more Palmitoyl-oleoyl-stearyl-glycerol (POS) than Piétrains. The percentages of SFA and MUFA decreased and the percentage of PUFA increased with time in FFA of Large White pigs. In Piétrains, similar changes were observed between days 1 and 5, but later the percentages of SFA increased and the percentage of PUFA decreased again. TBARS tended to increase with time particularly in Piétrains. Sarcoplasmic phospholipase A(2) decreased between days 5 and 9 in both breeds. Sarcoplasmic calcium was markedly higher at day 1 in Piétrains than in Large Whites then the difference decreased. These breed differences in lipid composition differences and lipid changes during storage are considered too small to be of practical importance, for instance in influencing the choice of a breed for pork production.     

Differential scanning calorimetry of lupin and soy proteins

Differential scanning calorimetry (DSC) was used to study the 7S and 11S globulin fractions extracted from lupin seed (Lupinus luteus) flour. In agreement with previous work on other lupin species, the isolate showed three denaturation peaks compared to the two observed with soy. By comparison with the isolated globulin fractions, the denaturation peaks at the two higher temperatures in the lupin isolate were assigned to the 11S and 7S globulins. The denaturation temperature of the lupin 7S globulin was about 10 K higher than that for the corresponding soy globulin, whereas the values for the 11S globulin were similar. All globulins displayed increasing thermal stability with decreasing moisture contents. Possible reasons for the differences in behaviour of soy and lupin protein isolates are discussed.     

Ripening‐related changes in the cell walls of olive (Olea europaea L.) pulp of two consecutive harvests

Olive fruits, harvested in two consecutive seasons at green, cherry and black stages, were used to study compositional changes in the cell walls during ripening. Ripening‐related changes in both harvests were characterised mainly by an increase in the solubilisation of pectic and hemicellulosic polysaccharides, an increase in the relative amount of arabinose in pectic polysaccharides and a decrease in the degree of methylesterification of pectic polysaccharides. Further to degrading processes, the data obtained suggest the synthesis of new polysaccharides. The analysis of olive cell wall phenolics showed mainly the presence of p‐coumaric acid, which increased in one harvest, whereas in the other the values did not differ. The samples of the second harvest, although presenting green, cherry and black colours, had less distinct ripening characteristics than those of the previous harvest. Different activity levels of polyphenol oxidase, polygalacturonase and pectin methylesterase might have contributed to the differences observed between the two harvests. The results showed the distinct extension of ripening‐related changes in the cell walls of the two harvests, indicating that the olive colour, although characteristic of the stage of ripening, cannot be strictly used for its evaluation and definition. Copyright © 2006 Society of Chemical Industry