Geochemical implications of trace elements and sulfur in the saturate, aromatic and resin fractions of crude oil from the Mara and Mara Oeste fields, Venezuela

Ten trace elements (Cr, Zn, Fe, Mn, Cu, Co, Ni, Mo, V and Sr) and sulfur were determined in the saturate, aromatic and resin fractions of 15 crude oils from Mara (DM) and Mara Oeste (DMO) fields of the Maracaibo Basin, Venezuela. The oils studied are classified as unaltered or altered by biodegradation. In the altered oil, the depletion of n-alkanes, the absence of isoprenoids and the presence of steranes and hopanes unaltered by biodegradation are indicative of moderate biodegradation. The elements Zn, Fe, Mn, Cu, Ni, and Sr were detected in the saturated hydrocarbon fraction; Cr and V were detected in the aromatic fraction in addition to the above elements; whereas the elements detected for the resin fraction were Cr, Zn, Fe, Cu, Ni, Mo, V, and Sr. Co was not detected in any fractions of the oils analyzed. Sulfur was found in all fractions of the oils studied. It was proposed that Fe, Zn, Sr, and Mn could have entered the oil during migration or Fe, Zn and Mn as pollutants during oil extraction. Cr and Cu may be of biological origin and Mo could be incorporated into the reservoir through bacteria. Only S, V, and Ni in the resin fractions can be used as indicators of the origin and correlation of Mara and Mara Oeste oils. Based on the results obtained in this work, it can be established that the V/(V+Ni) ratio in the resin fraction can be used as a correlation parameter, for these oils.     

Pomegranate fallen leaves as a source of natural dye for mordant-free dyeing of wool

The application of metal mordants is usually necessary in dyeing of wool with natural dyes to improve the dye exhaustion and fastness properties. The majority of metal salts generally used as mordants are considered as toxic and it is important to find replacements for them. Plant sources with high content of tannins are good candidates as bio-mordant or colourant to overcome this drawback. In this study, the waste fallen leaves of pomegranate tree were used as a source of natural dye for the eco-friendly dyeing of wool fabric without the use of metal mordants. The dyeing process variables including dye concentration, dyebath pH, and temperature were optimised using response surface methodology to obtain the highest colour strength. The colour strength was increased by increasing the natural dye powder up to 100%owf while the optimum pH and dyebath temperature were 4 and 100°C, respectively. The sample dyed under the optimal condition exhibited good fastness properties against washing and light. This study approved the potential of Punica granatum fallen leaves for the dyeing of wool without any mordant, while high fastness properties were obtained.     

Serendipitous Identification of a Covalent Activator of Liver Pyruvate Kinase

Enzymes are effective biological catalysts that accelerate almost all metabolic reactions in living organisms. Synthetic modulators of enzymes are useful tools for the study of enzymatic reactions and can provide starting points for the design of new drugs. Here, we report on the discovery of a class of biologically active compounds that covalently modifies lysine residues in human liver pyruvate kinase (PKL), leading to allosteric activation of the enzyme (EC₅₀=0.29 μM). Surprisingly, the allosteric activation control point resides on the lysine residue K282 present in the catalytic site of PKL. These findings were confirmed by structural data, MS/MS experiments, and molecular modelling studies. Altogether, our study provides a molecular basis for the activation mechanism and establishes a framework for further development of human liver pyruvate kinase covalent activators.     

Effect of zirconia tape porosity on fluorapatite surface film formation by dip coating

Thin fluorapatite (FA) layers on porous 3 mol% yttria-partially stabilized zirconia (Y-PSZ) substrates have been fabricated by dipping porous zirconia tapes into aqueous 27.4 vol% fluorapatite slurries. Two porous Y-PSZ tapes with different volume fraction of porosity were developed using an acrylic latex binder: tapes with 31.4 vol% porosity were prepared using 16.6 vol% starch as fugitive additive and those with 12.7 vol% porosity were fabricated without starch. The influence of the porous structure of the tape surfaces, top and bottom, on the casting rate and consequently on the layer thickness formed on each surface was studied. Layers formed on the top and bottom surfaces of the tapes with 12.7 and 31.4 vol% porosity were compared. The formation of a thin layer on the surface of the tape was governed by both liquid entrainment and slip casting mechanisms. The data for the FA layer formation were in good agreement with the slip casting model for immersion times>0. The casting rate at the top surface of both tapes was greater than that at the bottom surface. This difference was attributed to a greater porosity of the top surface with respect to that of the bottom one and was more pronounced for the tapes prepared with starch. Layers formed on the top surface were found to be about 55 and 32% thicker than those formed on the bottom surface for the tapes fabricated with and without starch, respectively. For the tapes prepared with starch, the greater porosity and number of smaller pores in the matrix of the top surface increased the casting rate and produced the thickest dip coated layers     

Rancidity development during the chilled storage of farmed Coho salmon (Oncorhynchus kisutch)

Coho salmon (Oncorhynchus kisutch) is a fatty fish species whose farming production has greatly increased in recent years. Lipid damage produced during Coho salmon chilled storage was studied for up to 24 d. Lipid hydrolysis (free fatty acids, FFA) and oxidation (conjugated dienes; peroxide value, PV; thiobarbituric acid index, TBA‐i; fluorescent compounds formation, FR; browning development) were determined and compared to lipid composition (polyene index, PI; astaxanthin, AX) changes and sensory assessment (rancid odour development) results. Most lipid damage indices developed slowly during storage; thus, values obtained for FFA, PV, TBA‐i and FR were in all cases under 1.5 g/100 g, 4.0 meq oxygen/kg lipid, 0.40 mg malondialdehyde/kg muscle and 0.40, respectively. Odour assessment showed a significant (p <0.05) rancidity development at day 10, when compared to starting fish material; then, non‐acceptable values were obtained at days 19 and 24. The PI analysis showed not many differences during the storage time, with the lowest mean value at day 19. AX analysis indicated a relatively high content in the white muscle, which was maintained till the end of the experiment. A low oxidation development is concluded for Coho salmon lipids when compared to other fatty fish species under the same chilling conditions. AX was found to contribute to the oxidation stability of Coho salmon lipids, due to its free radical scavenger properties.     

Nucleation behavior of blended high‐melting fractions of milk fat as affected by emulsifiers

The effect of highly hydrophobic emulsifiers, the palmitic sucrose ester P‐170 (hydrophilic/lipophilic balance (HLB) = 1.0), the stearic sucrose ester S‐170 (HLB = 1.0), the polyglycerol ester decaglycerol decastearate DAS 7S (HLB = 3.7) and the polyglycerol ester decaglycerol dodecabehenate DDB 750 (HLB = 2.6), on the nucleation of a high melting point milk fat fraction (HMF) and its blends with sunflower oil (SFO) was investigated by polarized laser light turbidimetry, X‐ray diffractometry and polarized light microscopy (PLM). Addition of polyglycerol esters accelerated nucleation, giving shorter induction times for the same supercooling. On the contrary, sucrose esters inhibited nucleation since induction times were elongated in all conditions selected. Addition of emulsifiers modified the polymorphic behavior in the blends with SFO. The β' form was promoted especially with the addition of S‐170. DAS 7S and DDB 750 promoted crystallization. PLM images showed many small crystals that did not appear in HMF images. Addition of P‐170 and S‐170 delayed nucleation and inhibited crystal growth. Crystals were notoriously smaller than the ones that appeared in HMF images. The Fisher–Turnbull model was used to calculate activation free energies of nucleation. In all cases, sucrose esters elevated the energy barrier for nucleation. Polyglycerol esters, however, if they had an effect on the energy barrier, lowered the values.     

Technological Implications of Modifying the Extent of Cell Wall-Proanthocyanidin Interactions Using Enzymes

The transference and reactivity of proanthocyanidins is an important issue that affects the technological processing of some fruits, such as grapes and apples. These processes are affected by proanthocyanidins bound to cell wall polysaccharides, which are present in high concentrations during the processing of the fruits. Therefore, the effective extraction of proanthocyanidins from fruits to their juices or derived products will depend on the ability to manage these associations, and, in this respect, enzymes that degrade these polysaccharides could play an important role. The main objective of this work was to test the role of pure hydrolytic enzymes (polygalacturonase and cellulose) and a commercial enzyme containing these two activities on the extent of proanthocyanidin-cell wall interactions. The results showed that the modification promoted by enzymes reduced the amount of proanthocyanidins adsorbed to cell walls since they contributed to the degradation and release of the cell wall polysaccharides, which diffused into the model solution. Some of these released polysaccharides also presented some reactivity towards the proanthocyanidins present in a model solution.     

Incorporation of polyfluorenes into poly(lactic acid) films for sensor and optoelectronics applications

Films of neat and plasticized biodegradable poly(lactic acid) (PLA) matrices containing anionic conjugated polyelectrolytes, poly[9,9‐bis(4‐phenoxybutylsulfonate)]fluorene‐2,7‐diyl‐alt‐arylenes, with 1,4‐phenylene and 4,4″‐p‐terphenylene, respectively, as arylene groups or a neutral poly(9,9‐dialkylfluorene) for comparison were prepared by solution casting. These films were characterized using differential scanning calorimetry, thermogravimetry, scanning electron microscopy and fluorescence spectroscopy. In addition, the effects of plasticizer on the thermal properties and the oxygen permeability of the PLA films were measured through the oxygen transmission rate. Results show that it is possible to obtain thin, optically transparent and luminescent films with potential in oxygen sensing, exhibiting good thermal and photochemical stability. At high polyelectrolyte content, evidence is found for phase separation and aggregate formation and it is no longer possible to obtain completely homogeneous films. The possibility of incorporating the cationic metal complex tris(2,2′‐bipyridyl)ruthenium(II) into plasticized PLA films containing conjugated polyelectrolytes for dual‐wavelength ratiometric luminescence sensing is also discussed. Copyright © 2012 Society of Chemical Industry     

Preparation and magnetoelectric properties of NiFe2O4–PZT composites obtained in-situ by gel-combustion method

Magnetoelectric composites of xNiFe₂O₄–(1 ? x)Pb(Zr,Ti)O₃ with x = 2, 5, 10, 20, 30% were prepared by citrate–nitrate combustion using PZT-based template powders. In order to ensure a better connectivity of dissimilar phases, we have used chemical methods for preparation in situ composites, followed by adequate sintering procedure. The structural, microstructural and functional properties of di-phase magnetoelectric composites of NiFe₂O₄–PZT are reported. The XRD analysis is demonstrating the synthesis of pure ferrite phase directly on the ferroelectric templates. An excellent mixing was obtained in the composite powders, as proved by a detailed SEM analysis.The magnetic and dielectric behaviors of the ceramic composites vary with the ratio of the two phases. The dielectric behavior is greatly influenced by the magnetic phase. The magnetoelectric (ME) coefficient was measured as a function of applied DC magnetic field. The maximum ME coefficient (dE/dH) varies from 0.0011 mV/(cm Oe) to 0.5 mV/(cm Oe) with increasing of NF addition.