Bisnaphthalimidopropyl Derivatives as Inhibitors of Leishmania SIR2 Related Protein 1

The NAD⁺‐dependent deacetylases, namely sirtuins, are involved in the regulation of a variety of biological processes such as gene silencing, DNA repair, longevity, metabolism, apoptosis, and development. An enzyme from the parasite Leishmania infantum that belongs to this family, LiSIR2RP1, is a NAD⁺‐dependent tubulin deacetylase and an ADP‐ribosyltransferase. This enzyme's involvement in L. infantum virulence and survival underscores its potential as a drug target. Our search for selective inhibitors of LiSIR2RP1 has led, for the first time, to the identification of the antiparasitic and anticancer bisnaphthalimidopropyl (BNIP) alkyl di‐ and triamines (IC₅₀ values in the single‐digit micromolar range for the most potent compounds). Structure–activity studies were conducted with 12 BNIP derivatives that differ in the length of the central alkyl chain, which links the two naphthalimidopropyl moieties. The most active and selective compound is the BNIP diaminononane (BNIPDanon), with IC₅₀ values of 5.7 and 97.4 μM against the parasite and human forms (SIRT1) of the enzyme, respectively. Furthermore, this compound is an NAD⁺‐competitive inhibitor that interacts differently with the parasite and human enzymes, as determined by docking analysis, which might explain its selectivity toward the parasitic enzyme.     

Ochratoxin A in wines,musts and grape juices from Spain

A survey on the occurrence of ochratoxin A (OTA) in 240 grape‐based beverages was carried out. Red and white wines from four different Spanish Designations of Origin (n = 160), musts (n = 20), grape juices (n = 10), ordinary wines (n = 20), special wines (Malaga, muscatel, sherry, vermouth, etc) (n = 20) and sparkling wines (n = 10) were assayed for OTA content using immunoaffinity column clean‐up and high‐performance liquid chromatography with fluorimetric detection (detection limit 0.05 µg l^?1). Forty‐three (17.9%) of the samples tested contained detectable levels of OTA. The overall mean OTA concentration in red and white wines of Designations of Origin was 0.30 and 0.18 µg l^?1 respectively (ranges 0.05–3.19 and 0.05–1.13 µg l^?1 respectively). The percentage of wine samples with detectable amounts of OTA was higher for red (18.3%) than for white (10%) wines. OTA was also found in two of 10 red ordinary wines (0.68 and 4.24 µg l^?1), whereas none of 10 white ordinary wines contained OTA. The mean OTA amount detected in sparkling wines was 0.44 µg l^?1 (range 0.14–0.71 µg l^?1). Two of 20 must samples contained OTA at low levels (0.08 and 0.18 µg l^?1), while none of 10 grape juice samples contained OTA. Highest amounts of OTA were found in special wines (45%), with a maximum of 15.25 µg l^?1 in a muscatel sample. Copyright © 2004 Society of Chemical Industry     

Changes in polyphenolic content and antioxidant activity after thermal treatments of grape seed extract and grape pomace

This study was undertaken to investigate the effect of heat treatment on polyphenolic content and antioxidant activity in grape pomace (GP) and grape seed extract (GSE). GP and GSE were heat treated in a furnace or autoclaved at 100 °C for 15, 30 and 60 min. Structural modifications of the polyphenols during thermal processes were determined by HPLC–MS, and the antioxidant activity was determined by ABTS, DPPH and photochemiluminescence methods. In general, furnace thermal treatment of GSE and GP did not affect the total extractable polyphenols content, tannin content, procyanidin components and the antioxidant activity. Autoclave treatment caused an extensive hydrolysis of gallocatechin (70%), catechin (61%), epicatechin (65%), procyanidin B1 (75%) and procyanidin B2 (73%) in GSE, and an increase in gallic acid (71%), gallocatechin (100%) and epicatechin gallate (129%) in GP. Autoclave treatment did not affect the antioxidant activity of GSE or GP. It can be concluded that the effect of autoclave was more severe than furnace heat treatment modifying the phenolic profile in a different manner depending on the grape seed product used. These modifications were not related with changes in antioxidant activity.     

Interfacial Tension; a Stabilizing Factor for Janus Emulsions of Silicone Bixa Orellana Oils

The destabilization process was investigated for a Janus emulsion of silicone and Bixa Orellana oils stabilized by polyoxyethylene sorbitan monooleate (Tw 80) and carboxymethyl cellulose. The emulsion stabilized with Tw 80 showed significant and fast creaming, a process that was prevented by the addition of the polymer. During the extensive coalescence of the emulsions stabilized by Tw 80, the Janus topology was retained for months of storage until, finally, separation of the oils occurred. This result strongly indicates an unexpected stabilizing action of the i nterfacial free energy. This conclusion was supported by a calculation for a realistic model system of the interfacial energy difference between two cases of coalescence. In the first case, the two coalescing Janus drops united into a larger Janus drop, while in the second case two drops formed, each with only one oil. The first case gave a spontaneous reaction (reduced interfacial energy), while the second one meant an increase of energy, i.e. it cannot happen without adding energy. The authors are aware that this stabilization is a new phenomenon in emulsion science with potential ramifications in future emulsion technology. However, it is essential to realize that the stabilization is of temporary occurrence in the destabilization process, and the free energy to give a final emulsion state with separated oils is overwhelmingly dominant. In short, Janus emulsions will, in the end, separate into layers of the liquids, like all emulsions.     

How much nitrogen is fixed by biological symbiosis in tropical dry forests? 1. Trees and shrubs

Despite the recognized importance of the process, estimates of the amount of nitrogen fixed by biological symbiosis in tropical dry forests are almost nonexistent. We estimated the nitrogen fixed annually by the leaves of trees and shrubs at sites regenerating for 16 and 38?years and in an old-growth dry forest using ¹⁵N abundance methodology. The total leaf biomass (1,824?C3,036?kg?ha^?1) and nitrogen contents (62?C90?kg?ha^?1) did not differ among the areas. In all of the areas, most of the leaf biomass belonged to legume plants, but the proportion of the N₂-fixing legumes decreased with increasing regeneration time. In the 16-year regenerating area, almost all of the N was in the leaves of the N-fixing Mimosa tenuiflora plants, but fixation was absent or very low as it was in the N-fixing species present in the 38-year regenerating area. In the old-growth Caatinga, all of the N-fixing species (M. tenuiflora, Piptadenia stipulacea and Anadenanthera colubrina) had large proportions (47?C62?%) of their N derived from atmospheric N₂, but the amount of fixed N (6?kg?ha^?1) was a small proportion of the total leaf N because these plant species were a small part of the vegetation. The total input of biologically fixed N to the old-growth forest was similar in magnitude to an estimate made for a humid tropical forest in Amazonia.     

Characteristics of menhaden oil ethanolysis by immobilized lipase in supercritical carbon dioxide

Ethanolysis of menhaden oil was performed with 1,3-regiospecific lipase to produce diglycerides and monoglycerides containing polyunsaturated fatty acids, and fatty acid ethyl esters. Immobilized lipases like lipozyme TL-IM (Thermomuces lanuginosa immobilized on silica gel) were used for enzymatic ethanolysis. Ethanolysis was carried out in different processes (solvent free, organic solvent and supercritical fluid system) to compare the reaction rate and yield obtained by menhaden oil ethanolysis. Organic solvent (hexane) and supercritical carbon dioxide (SC-CO₂) were used as reaction medium. The reaction products were analyzed by gas chromatography (GC), thin layer chromatography (TLC) and high performance liquid chromatography (HPLC). Higher amounts of ethanol as a substrate caused substrate inhibition which dramatically decreased the reaction rate of ethanolysis. To elucidate the effect of pressure, enzymatic ethanolysis was performed in SC-CO₂ at pressures ranging from 75 to 121 bar. Enzymatic ethanolysis of menhaden oil in SC-CO₂ decreased by substrate inhibition. Reaction rate and optimum amount of ethanol used were depended on SC-CO₂ density individually. Kinetic model with substrate inhibition (dead-end inhibition) by excess ethanol was set up to measure the reaction and inhibition rates.     

Piezoresponse force microscopy characterization of rare-earth doped BiFeO3 thin films grown by the soft chemical method

The multiferroic behavior with ion modification using rare-earth cations on crystal structures, along with the insulating properties of BiFeO₃ (BFO) thin films was investigated using piezoresponse force microscopy. Rare-earth-substituted BFO films with chemical compositions of (Bi_1.00−xRE_xFe_1.00O₃ (x=0; 0.15), RE=La and Nd were fabricated on Pt (111)/Ti/SiO₂/Si substrates using a chemical solution deposition technique. A crystalline phase of tetragonal BFO was obtained by heat treatment in ambient atmosphere at 500 °C for 2 h. Ion modification using La³⁺ and Nd³⁺ cations lowered the leakage current density of the BFO films at room temperature from approximately 10⁻⁶ down to 10⁻⁸ A/cm². The observed improved magnetism of the Nd³⁺ substituted BFO thin films can be related to the plate-like morphology in a nanometer scale. We observed that various types of domain behavior such as 71° and 180° domain switching, and pinned domain formation occurred. The maximum magnetoelectric coefficient in the longitudinal direction was close to 12 V/cm Oe.     

Changes in the milk and cheese fat composition of ewes fed commercial supplements containing linseed with special reference to the CLA content and isomer composition

A study was carried out to increase the CLA contents in ewes’ milk fat under field conditions by dietary means and to investigate the extent of the changes and consequences for milk processing and cheese quality. During a 3-mon period, ewes’ bulk milk samples were collected every week from two different herds. For the first 4 wk the ewes were fed a conventional diet. Then the following 6 wk a supplement enriched in α-linolenate (whole linseed) was incorporated into the ovine diet. Finally, in the last 3 wk the feeding was the same as in the first 4 wk. The FA profile in milk fat was monitored by GC, and the distribution of CLA isomers was thoroughly tested by combining GC-MS of 4,4-dimethyloxazoline derivatives (DMOX) with silver ion-HPLC (Ag⁺-HPLC) of FAME. Reconstructed mass spectral profiles of CLA characteristic ions from DMOX were used to identify positional isomers, and Ag⁺-HPLC was used to quantify them. An increase in total CLA in milk fat was observed, and total CLA remained elevated during the weeks of enriched α-linolenate feeding. In our experimental conditions there was a linear relationship between trans-vaccenic acid (trans-11-octadecenoic acid; trans-11 18∶1) and 9-cis, 11-trans CLA in ewes’ milk fat. Concerning the CLA isomer profile, increases in the 11,13- and 12,14–18∶2 positional isomers were considerable when linseed was included in the diet. Organoleptic characteristics of cheeses made with CLA-enriched milk did not substantially differ from those made with nonsupplemented ewes’ milk. CLA total content and isomer profile did not change during ripening.     

Discriminating power of the hydrocarbon content from virgin olive oil of extremadura cultivars

Samples of virgin olive oils (105) from seven Extremaduran olive varieties (Cacereña, Carrasqueña, Cornezuelo, Corniche, Morisca, Picual, and Verdial de Badajoz) in three stage of maturity (green, semi-ripe, and ripe) were collected and the alkane, alkene, and sesquiterpene contents determined. There were significant differences at the 0.01 probability level in most of the hydrocarbons, both by variety and by state of maturity. Discriminant analysis applied to 70 samples explained 72.3% of the variance between the different groups of varieties and allowed 90% of the samples to be classified according to their variety. The acceptability of the model was verified against the remaining 35 samples, giving a mean level of correct classification of 94%.     

Influence of chemical structure of hardener on mechanical and adhesive properties of epoxy polymers

The mechanical and adhesive properties of epoxy formulations based on diglycidyl ether of bisphenol A cured with various aliphatic amines were evaluated in the glass state. Impact and uniaxial compression tests were used to determine the impact energy, elastic modulus and yield stress, respectively. The adhesion tests were carried out in steel–steel joints using single‐lap shear, T‐peel, and impact adhesive joints geometry. The better mechanical and adhesive behavior of the networks is obtained when exists high flexibility of chain between crosslink and/or high elastic modulus. The 1‐(2‐aminoethyl)piperazine epoxy network presents the best adhesive properties, high flexibility, and the largest impact energy. However, it possesses low elastic modulus and yield stress. Also, exhibits increases in peel strength and impact energy while reductions in lap shear strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010