Trifunctional Squaramide Catalyst for Efficient Enantioselective Henry Reaction Activation

A new class of trifunctional squaramide catalyst acting by means of multiple interactions has been found in a study of the Henry reaction. Enantiomerically enriched nitroaldol products were obtained in good yields and high enantioselectivities under mild conditions using one of the smallest amounts of organocatalyst reported so far for this reaction (0.25 mol%). The catalyst was able to generate hydrogen bonding and anion‐π/hydrogen‐π interactions with the substrates, responsible of the improvement in the reactivity and the enantioselectivity of this process. Computational calculations support a mechanistic hypothesis based on an anion‐π effect, this being the first example reported in asymmetric catalysis.

     

Structural and Functional Basis for Understanding the Biological Significance of P2X7 Receptor

The P2X7 receptor (P2X7R) possesses a unique structure associated to an as yet not fully understood mechanism of action that facilitates cell permeability to large ionic molecules through the receptor itself and/or nearby membrane proteins. High extracellular adenosine triphosphate (ATP) levels—inexistent in physiological conditions—are required for the receptor to be triggered and contribute to its role in cell damage signaling. The inconsistent data on its activation pathways and the few studies performed in natively expressed human P2X7R have led us to review the structure, activation pathways, and specific cellular location of P2X7R in order to analyze its biological relevance. The ATP-gated P2X7R is a homo-trimeric receptor channel that is occasionally hetero-trimeric and highly polymorphic, with at least nine human splice variants. It is localized predominantly in the cellular membrane and has a characteristic plasticity due to an extended C-termini, which confers it the capacity of interacting with membrane structural compounds and/or intracellular signaling messengers to mediate flexible transduction pathways. Diverse drugs and a few endogenous molecules have been highlighted as extracellular allosteric modulators of P2X7R. Therefore, studies in human cells that constitutively express P2X7R need to investigate the precise endogenous mediator located nearby the activation/modulation domains of the receptor. Such research could help us understand the possible physiological ATP-mediated P2X7R homeostasis signaling.     

BIRC6 Is Associated with Vulnerability of Carotid Atherosclerotic Plaque

Carotid atherosclerotic plaque rupture can lead to cerebrovascular accident (CVA). By comparing RNA-Seq data from vascular smooth muscle cells (VSMC) extracted from carotid atheroma surgically excised from a group of asymptomatic and symptomatic subjects, we identified more than 700 genomic variants associated with symptomatology (p < 0.05). From these, twelve single nucleotide polymorphisms (SNPs) were selected for further validation. Comparing genotypes of a hospital-based cohort of asymptomatic with symptomatic patients, an exonic SNP in the BIRC6 (BRUCE/Apollon) gene, rs35286811, emerged as significantly associated with CVA symptomatology (p = 0.002; OR = 2.24). Moreover, BIRC6 mRNA levels were significantly higher in symptomatic than asymptomatic subjects upon measurement by qPCR in excised carotid atherosclerotic tissue (p < 0.0001), and significantly higher in carriers of the rs35286811 risk allele (p < 0.0001). rs35286811 is a proxy of a GWAS SNP reported to be associated with red cell distribution width (RDW); RDW was increased in symptomatic patients (p < 0.03), but was not influenced by the rs35286811 genotype in our cohort. BIRC6 is a negative regulator of both apoptosis and autophagy. This work introduces BIRC6 as a novel genetic risk factor for stroke, and identifies autophagy as a genetically regulated mechanism of carotid plaque vulnerability.     

Sending Mixed Messages: A Trophic Cascade Produced by a Belowground Herbivore-Induced Cue

Plants defend themselves against herbivores both directly (chemical toxins and physical barriers) and indirectly (attracting natural enemies of their herbivores). Previous work has shown that plant roots of citrus defend against root herbivores by releasing an herbivore-induced plant volatile (HIPV), pregeijerene (1,5-dimethylcyclodeca-1,5,7-triene), that attracts naturally occurring entomopathogenic nematodes (EPNs) to Diaprepes abbreviatus larvae when applied in the field. However, the soil community is complex and contains a diversity of interspecific relationships that modulate food web assemblages. Herein, we tested the hypothesis that other nematode types beyond EPNs, as well as, nematophagous fungi are affected by the same HIPV that attracts EPNs to herbivore-damaged roots. We employed molecular probes designed to detect and quantify nematodes from the Acrobeloides–group (free-living bacterivorous nematodes, FLBNs), some of which compete with EPNs by ‘hyperparasitizing’ insect cadavers, and five species of nematophagous fungi (NF), which attack and kill EPNs. In two different agricultural systems (citrus and blueberry), we detected diverse species of nematodes and fungi; however, only the behavior of FLBNs was affected in a manner similar to that reported previously for EPNs. Although detected, NF abundance was not statistically affected by the presence of the belowground HIPV. We provide the first evidence showing subterranean HIPVs behave much the same as those aboveground, attracting not only parasitoids, but also hyperparasites and other food web members.     

Effect of adhesive application on the shear bond strength of flowable composite resins and APC plus to orthodontic molar tubes

Objectives: To evaluate the effect of adhesive application on the shear bond strength (SBS) of orthodontic tubes to acid-etched human enamel when using different flowable composite resins and the APC Plus system (APC). Study design: One hundred metal tubes were bonded to human third molars, which were randomly divided into five groups: Tetric EvoFlow (TF); Wave mv Flow (W); Transbond Supreme LV (S); Transbond XT (XT); and APC. For each experimental group, half of the specimens were bonded in combination with Transbond XT adhesive. After 72?h, an SBS test was performed using a universal testing machine. Two-way analysis of variance (ANOVA) was run for multiple comparison tests and for comparing the mean SBS among the 10 subgroups to evaluate the effect of both the composite and the adhesive factors. Then, a Student-Newman-Keuls test was used for pairwise comparisons using the highest mean SBS group as reference. Adhesive Remnant Index scores were determined for the teeth after failure and compared by χ ²-test. Two representative molar surfaces from the 10 subgroups were assessed under scanning electron microscope. Results: The application of adhesive did not have a significant effect, but there was a marked tendency toward the influence of the factor composite on SBS. The mean SBS of tubes bonded with XT with adhesive was significantly higher than that of those bonded with APC with adhesive, TF with and without adhesive, and S with adhesive. Conclusion: Flowable composites and the APC system without intermediate bonding resin could be conveniently applied for orthodontic tube bonding.     

Evolution of the pozzolanic activity of a thermally treated zeolite

Zeolites generally show pozzolanic activity due to their structural characteristics. The utilisation of pozzolans as additions to cements results in added technical advantages of the construction materials. In this study, the pozzolanic activity of a thermally treated natural mordenite-type zeolite from the Palmarito open-air deposit (Cuba) was evaluated with respect to a non-treated zeolite. Initially, a thermal treatment of the zeolite was performed at different temperatures within the range 300–1000 °C for 5 h in order to evaluate the better temperature of treatment. Afterwards, the pozzolanic activity was determined for each temperature after 7 days of reaction with a saturated Ca(OH)₂ solution that simulates the release of lime from ordinary Portland cement during the hydration reaction. The higher pozzolanic activity was achieved with the thermal treatment performed at 300 °C. Therefore, a further study studied the evolution of the mineralogical phases produced during pozzolanic reaction up to 90 days, carried out with the zeolite treated at that temperature. Consumption of Ca²⁺ in solution and formation of C–S–H-like phases with low Ca/Si ratio were experimentally observed as the main pozzolanic products. The thermodynamic study confirms high reactivity of the zeolite at short-term and chemical stability of the reaction products after 28 days. The zeolite thermally treated at 300 °C confirmed an increase in the pozzolanic activity with respect to the non-treated zeolite.     

Nitrile rubber/organomontmorillonite nanocomposites produced by solution and melt compounding: Effect of the polarity of the quaternary ammonium intercalants

A comparative study of the development of nitrile rubber (NBR) based nanocomposites was performed; two organomontmorillonites (Cloisite 15A and Cloisite 30B) and two procedures for clay dispersion (melt blending and solution intercalation) were used. The nanocomposites were cured with a system based on dicumyl peroxide in the presence of m‐phenylenebismaleimide as a coagent for curing. The dispersion of the organoclay inside the NBR matrix was investigated with transmission electron microscopy and X‐ray diffraction. All the cured systems displayed a combination of intercalated, partially exfoliated clay platelets and confined, deintercalated clay; the degree of dispersion depended on the amount of clay, the type of intercalant, and the intercalation procedure. The highest amount of intercalated/exfoliated clay was obtained with a previous dispersion of the clay (Cloisite 30B) in an NBR solution. All the nanocomposites presented outstanding tensile strength and creep response, and this indicated a reinforcing effect of the layered silicates. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Economic Optimized Medium for Tensio-Active Agent Production by Candida sphaerica UCP0995 and Application in the Removal of Hydrophobic Contaminant from Sand

Statistical experimental designs and response surface methodology were employed to optimize the concentrations of agroindustrial residues as soybean oil (SORR) from refinery, and corn steep liquor (CSL) from corn industry, for tensio-active agent produced by Candida sphaerica UCP 0995. Three 2² full factorial design were applied sequentially to investigate the effects of the concentrations and interactions of soybean oil refinery residue and corn steep liquor on the surface tension of free-cell culture broth for 144 h. Two 2² central composite designs and response surface methodology were adopted to derive a statistical model to measure the effect of SORR and CSL on the surface tension of the free-cell culture broth for 144 h. The regression equation obtained from the experimental data using a central composite design was solved, and by analyzing the response surface contour plots, the optimal concentrations of the constituents of the medium were determined: 8.63% v/v (≅9% v/v) of SORR and 8.80% v/v (≅9% v/v) CSL. The minimum surface tension predicted and experimentally confirmed was 25.25 mN/m. The new biosurfactant, denominated Lunasan, recovered 95% of motor oil adsorbed in a sand sample, thus showing great potential for use in bioremediation processes, especially in the petroleum industry.     

A wind–diesel system with hydrogen storage: Joint optimisation of design and dispatch

We compare two models to determine the size of grid units and dispatch in a wind-diesel power system with hydrogen storage. Both take as data 1-year time series of hourly wind speed and electricity demand, and their objective is to minimise cost. Our first model, based on linear programming, generates as output a combination of capacities and a year time series for the dispatch variables. Our second model runs a fixed dispatch rule over several capacity combinations and selects the cheapest option. The dispatch rule can then be improved through comparison with the linear programming solution. At present costs, the hydrogen storage-conversion system is excluded from the solutions, so the interesting operation rules associated with the option of harvesting do not arise. However, the costs of hydrogen storage technologies are decreasing with investment. By running our model with prospective costs for year 2010, we see storage emerge in the optimum, and thus a sample of the operation patterns that will occur in a renewable dominated grid.