Mannich-Type reactions in the Gas-Phase: the addition of Enol Silanes to cyclic N-Acyliminium Ions

The intrinsic gas-phase reactivity of cyclic N-acyliminium ions in Mannich-type reactions with the parent enol silane, vinyloxytrimethylsilane, has been investigated by double- and triple-stage pentaquadrupole mass spectrometric experiments. Remarkably distinct reactivities are observed for cyclic N-acyliminium ions bearing either endocyclic or exocyclic carbonyl groups. NH-Acyliminium ions with endocyclic carbonyl groups locked in s-trans forms participate in a novel tandem N-acyliminium ion reaction:  the nascent adduct formed by simple addition is unstable and rearranges by intramolecular trimethylsilyl cation shift to the ring nitrogen, and an acetaldehyde enol molecule is eliminated. An NSi(CH3)3-acyliminium ion is formed, and this intermediate ion reacts with a second molecule of vinyloxytrimethylsilane by simple addition to form a stable acyclic adduct. N-Acyl and N,N-diacyliminium ions with endocyclic carbonyl groups, for which the s-cis conformation is favored, react distinctively by mono polar [4+ + 2] cycloaddition yielding stable, ressonance-stabilized cycloadducts. Product ions were isolated via mass-selection and structurally characterized by triple-stage mass spectrometric experiments. B3LYP/6-311G(d,p) calculations corroborate the proposed reaction mechanisms.

The Addition of Allyltrimethylsilane to Cyclic N-Acyliminium Ions Derived from (S)-(+)-Mandelic Acid and Cyclohexyl-Based Chiral Auxiliaries

A adição de aliltrimetilsilano, promovida por TiCl4, a íons N-aciliminios cíclicos de 5- e 6-membros derivados do ácido (S)-(+)-mandélico, (1R,2S)-trans-2-fenil-1-cicloexanol e (1R,2S,5R)-8-fenilmentol ocorreu com baixas a moderadas razões diastereoisoméricas (1:1-6:1) e forneceu as respectivas amidas e carbamatos em bons rendimentos. A melhor diastereosseleção facial foi observada com o uso de (1R,2S,5R)-8-fenilmentol como auxiliar quiral. As amidas e carbamatos 2-substituídos foram convertidos nos alcalóides (S)- e (R)-propil pirrolidina e coniina com eficiente recuperação dos auxiliares quirais.

Mitigation of sea level rise effects by addition of sediment to shrimp ponds

In New Caledonia barren salt-pans located landward to mangroves are used for the construction of shrimp ponds. The existing farms are jeopardized by the projected rise in the sea level, because the landward boundaries of ponds are situated at the elevation reached by spring tides. One low-cost strategy for mitigating the effects of sea level rise is to raise the level of the bottom of ponds. To test the effectiveness of such an adaptation, we built 4 experimental ponds in the low-lying zone of an existing 10 ha shrimp pond. The level of the bottom of 2 ponds was raised by adding about 15 cm of agricultural soil. Placing agricultural soil in the pond did not impair the functioning of the shrimp pond ecosystem. On the contrary, it resulted in unexpectedly better shrimp production in the 2 ponds with agricultural soils versus control ponds. We conclude that placing a layer of soil inside shrimp ponds is a promising strategy for maintaining the viability of shrimp ponds as the sea level rises.

Value addition to mollusc shells for income generation

The poster explains how to make value additions to mollusc shells for income generation among the fishing communities of Lake Victoria, Uganda

Composts addition may improve biology in cotton soils

Composts can provide a source of organic carbon and nutrients for soil biota and increase soil fertility as well as provide other biological and structural benefits hence compost addition to cotton soils is seen as a way to improve cotton soil biological health and fertility. In a six month incubation experiment we analysed the changes in microbial populations and activities related to C and N cycling following the application of feedlot, poultry manure and gin trash compost materials. A significant variation in the chemical composition, e.g. major nutrients and trace elements, was found between the three compost products. The feedlot compost generally contained higher levels of dissolved organic carbon, total nitrogen and bicarbonate extractable phosphorus whereas the Gin trash compost had lower carbon and nutrient concentrations. The effect of compost addition @ 5 and 10t/ha generally increased microbial activity but the effect was only evident during the first two weeks of incubation. Composts effects on the abundance of total bacteria (16S), nitrifying (amoA), nitrogen fixing (nifH) and denitrifying bacteria (nosZ) and total fungi (ITS gene) varied between different composts. The addition of feedlot and poultry compost material significantly increased the levels of dissolved organic carbon (DOC) and nitrogen (DON) in soil compared to that in control soils while ‘Gin trash’ compost had no effect. These differences reflected in the microbial catabolic diversity changes in the compost amended soils. Therefore, chemical analysis of the compost material before application is recommended to more fully consider its’ potential benefits.

Colour differentiation of high-lycopene tomato fruit through the addition of the colourless-epidermis (y) mutation

High-lycopene tomatoes (Solanum lycopersicum) are characterised by an intense red flesh-colour, due to an elevated concentration of the carotenoid, lycopene. However, this characteristic is only visible once fruit are cut open, making it impossible to differentiate intact high-lycopene fruit from standard tomato fruit, a clear market disadvantage. The reason that fruit colour of both high-lycopene and standard fruit looks almost identical from the outside is because tomato fruit normally contain the yellow flavonoid 'naringenin chalcone' in a thin layer of epidermal cells. It is this combination of naringenin chalcone and the underlying lycopene in the flesh that gives tomatoes their characteristic orange-red colour. By incorporation of the recessive colourless epidermis mutant allele 'y' (which prevents naringenin chalcone accumulation) into high-lycopene fruit, we have been able to create high-lycopene tomatoes (hp1.ogc.y) exhibiting a deep-pink colour visible from the outside. Hue angle of the skin of the high-lycopene 'y' mutant and a regular highlycopene tomato (hp1.ogc.Y) was 30 and 38°, respectively, while flesh values were similar at 31 and 32°, respectively. Removal of naringenin chalcone from the epidermis appeared to improve the visibility of underlying lycopene, such that fruit outer colour became a subsequent indicator of underlying flesh colour. The removal of epidermal pigmentation means that high-lycopene fruit can now be differentiated from standard tomato fruit in the market place without the need to cut fruit open.

Ultrasound-assisted extraction of R-phycoerythrin from Grateloupia turuturu with and without enzyme addition

The aim of this study was to compare two processes for the extraction of R-phycoerythrin (R-PE) from the red seaweed Grateloupia turuturu: ultrasound-assisted extraction (UAE) and ultrasound-assisted enzymatic hydrolysis (UAEH). Process efficiencies were both evaluated by the yield of R-PE extraction and by the level of liquefaction. Experiments were conducted at 40 and 22 °C, for 6 h, using an enzymatic cocktail and an original ultrasonic flow-through reactor. R-PE appeared very sensitive to temperature, thus 22 °C is strongly recommended for its extraction by UAEH or UAE. However, the higher processing temperature (40 °C) clearly increased the extraction of water-soluble compounds (up to 91% of liquefaction). These two new processes are thus promising alternatives for the extraction of water-soluble components including R-PE, from wet seaweeds, with extraction yields at least similar to conventional solid–liquid extraction.

Water Quality Impacts due to the Addition of Biosolids-Derived Compost to Bioretention

Bioretention is a common stormwater control measure (SCM). While compost, combined with other bioretention soil media (BSM), has the potential for increased pollutant and water uptake and storage, it also may leach harmful nutrients. Limited information is available on the use of compost in SCMs. Therefore, this project seeks to analyze the impacts of the addition of biosolids-derived compost to bioretention. To accomplish this, bioretention mesocosm column studies were conducted to determine the leaching effects of 15%, 30%, and 30% tap water-washed compost, mixed with standard BSM. Synthetic storm runoff was applied to the columns and the effluent was analyzed for total nitrogen (N), phosphorus (P), and their speciation. All three columns leached N and P with maximum total N concentrations of 2,200, 2,100, and 300 mg-N/L and total P concentrations of 12, 4.9, and 4.6 mg-P/L for the 30%, 15%, and 30% washed mesocosms, respectively. Therefore, based on this study, it is not recommended that biosolids-derived compost be added to bioretention media.

Dimensional stability of an addition silicone after disinfection/sterilization

Poster presented at the “From Basic Sciences to Clinical Research” – First International Congress of CiiEM. Egas Moniz, Caparica, Portugal, 27-28 November 2015

Dimensional change of two addition silicones

Poster apresentado no XXIV Congresso da Ordem dos Médicos Dentistas. Lisboa, 12-14 Novembro 2015

Platinum–rhodium–tin/carbon electrocatalysts for ethanol oxidation in acid media: effect of the precursor addition order and the amount of tin

Carbon-supported Pt x –Rh y –Sn z catalysts (x:y:z = 3:1:4, 6:2:4, 9:3:4) are prepared by Pt, Rh, and Sn precursors reduction in different addition order. The materials are characterized by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy techniques and are evaluated for the electrooxidation of ethanol in acidic media by cyclic voltammetry, chronoamperometry, and anode potentiostatic polarization. The influence of both the order in which the precursors are added and the composition of metals in the catalysts on the electrocatalytic activity and physico-chemical characteristics of Pt x –Rh y –Sn z /C catalysts is evaluated. Oxidized Rh species prevail on the surface of catalysts synthesized by simultaneous co-precipitation, thus demonstrating the influence of synthesis method on the oxidation state of catalysts. Furthermore, high amounts of Sn in composites synthesized by co-precipitation result in very active catalysts at low potentials (bifunctional effect), while medium Sn load is needed for sequentially deposited catalysts when the electronic effect is most important (high potentials), since more exposed Pt and Rh sites are needed on the catalyst surface to alcohol oxidation. The Pt3–Rh1–Sn4/C catalyst prepared by co-precipitation is the most active at potentials lower than 0.55 V (related to bifunctional effect), while the Pt6–Rh2–Sn4/C catalyst, prepared by sequential precipitation (first Rh and, after drying, Pt + Sn), is the most active above 0.55 V.

Effects of solid poly (ethylene glycols) addition to the solutions of aniline or N,N-dimethylaniline with water:experimental measurements and modelling

In this work, the liquid-liquid and solid-liquid phase behaviour of ten aqueous pseudo-binary and three binary systems containing polyethylene glycol (PEG) 2050, polyethylene glycol 35000, aniline, N,N-dimethylaniline and water, in the temperature range 298.15-350.15 K and at ambient pressure of 0.1 MPa, was studied. The obtained temperature-composition phase diagrams showed that the only functional co-solvent was PEG2050 for aniline in water, while PEG35000 even showed a clear anti-solvent effect in the N,N-dimethylaniline aqueous system. The experimental solid-liquid equilibria (SLE) data have been correlated by the non-random two-liquid (NRTL) model, and the correlation results are in accordance with the experimental results.