Efficient Modular Synthesis of Isomeric Mono‐ and Bispyridyl[2.2]paracyclophanes by Palladium‐Catalyzed Cross‐ Coupling Reactions

Pyridyl‐substituted [2.2]paracyclophanes build a multifunctional structural motif that is useful in material chemistry, catalysis and for luminescent structures. Nonetheless, there is still a lack of general methods for the synthesis of these structures tolerating easily accessible bromides as well as different isomeric pyridyl groups. Hence the coupling of functionalized [2.2]paracyclophanes with various substituted and functionalized pyridyl derivatives was achieved using Stille, Suzuki and Kumada coupling conditions. Hereby the Stille coupling of a [2.2]paracyclophane is presented as a versatile reaction for the formation of heteromeric [2.2]paracyclophane‐containing biaryl structures.

     

Relevance of the acid–base approach in prediction of adhesion properties in two‐component injection moulding

We demonstrate the use of innovative wetting method in prediction of the adhesion properties of biobased polymers for two‐component injection moulding, taking into account the acid–base surface properties of joined materials. The measurements were carried out in accordance with modified Berger method by calculation of the difference in shortened acidity parameter ΔD_short between hard and soft component. Correlation factors up to 0.99 were observed between ΔD_short and peel force. In comparison to results obtained by conventional wetting methods, high potential for the selection of components with high interface adhesion and for prediction of the functionality by the acid–base approach was demonstrated. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43048.     

Subsoil <Superscript>15</Superscript>N-N<Subscript>2</Subscript>O Concentrations in a Sandy Soil Profile After Application of <Superscript>15</Superscript>N-fertilizer

Studies on emissions of nitrous oxide (N₂O) from agricultural soils mostly focus on fluxes between the soil and the atmosphere or are limited to the atmosphere in the topsoil. However, in soils with shallow water tables, significant N₂O formation may occur closer to the groundwater. The aims of this study were (i) to determine the importance of subsoil N₂O formation in a sandy soil; and (ii) to obtain a quantitative insight in the contribution of subsoil N₂O to the overall losses of N₂O to the environment. We applied ¹⁵N labeled fertilizer at a rate of 5.22 kg ¹⁵N ha⁻¹; 50% as Ca(NO₃)₂ and 50% as NH₄Cl, on a mesic typic Haplaquod seeded with potatoes (Solanum tuberosum L.), and traced soil N₂O concentrations and fluxes over a one-year period. Throughout the year, total N₂O and the amount of ¹⁵N recovered in soil N₂O were highest in the subsoil, with a maximum concentration at 48 cm depth in mid-February of 19900 μl m⁻³ and 24 μg ¹⁵N m⁻³, respectively. The maximum concentration coincided with the highest water-filled pore space of 71%. The cumulative flux of N₂O was 446 g N₂O-N ha⁻¹, the recovery of ¹⁵N in this flux was 0.06%. During the summer, maximum fluxes followed high soil N₂O concentrations. During winter, no such relation was found. We concluded that the formation of N₂O was the highest in the subsoil, largely controlled by water-filled pore space rather than NO₃⁻ concentration or temperature. Although high subsoil N₂O concentrations did not lead to high surface fluxes of N₂O in the winter, artificial draining may lead to high indirect N₂O emissions through supersaturated drainage water.     

Destabilization of the Emulsion Formed during Aqueous Extraction of Soybean Oil

Characterization and destabilization of the emulsion formed during aqueous extraction of oil from soybean flour were investigated. This emulsion was collected as a cream layer and was subjected to various single and combined treatments, including thermal treatments and enzymatic treatments, aimed at recovery of free oil. The soybean oil emulsion formed during the aqueous extraction processing of full fat flour contains high molecular weight glycinin and β-conglycinin proteins and smaller oleosin proteins, which form a multilayer interface. Heat treatment alone did not modify the free oil recovery but freeze–thaw treatment increased the oil yield from 3 to 22%. After enzymatic treatment of the emulsion, its mean droplet size changed from 5 to 14 μm and the oil recovery increased to 23%. This increase could be attributed to the removal (due to enzymatic hydrolysis) of large molecular weight polypeptides from the emulsion interface, resulting in partial emulsion destabilization. When enzymatic treatment was followed by a freeze–thaw step, the oil recovery increased to 46%. This result can be attributed to the thinner interfacial membrane after enzymatic hydrolysis, partial coalescence during freeze–thaw, and coalescence during centrifugation. Despite the reduction in emulsion stability achieved, additional demulsification approaches need to be pursued to obtain an acceptably high conversion to free oil.     

High-throughput approach to the catalytic combustion of diesel soot

A methodology for the evaluation of diesel soot oxidation catalysts by high-throughput (HT) screening was developed. The optimal experimental conditions (soot amount, catalyst/soot ratio, type of contact, composition and flow rate of gas reactants) ensuring a reliable and reproducible detection of light-off temperatures in a 16 parallel channels reactor were set up. The temperature profile measured in the catalyst/soot bed under TPO conditions when the exothermic combustion of soot takes place was shown to provide an accurate measurement of the ignition. Its reproducibility and relevance were checked. The results obtained with a reference noble metal free catalyst (La_0.8Cr_0.8Li_0.2O₃ perovskite) agree very well with literature data. Qualitative mechanistic features could be derived from these experiments, stressing the likely limiting step of oxygen transfer from catalyst surface to soot particulates to ignite the soot combustion. Ceria material was shown to be more appropriate than perovskite one. From an HT screening of a large diverse library (over 100 mixed oxides catalysts) under optimized conditions, about 10 new formulations were found to perform better than selected noble metal free reference materials.     

Possible impacts of floods and droughts on water quality

The gradual climate change symptoms in many places on Earth have been observed during the last 20 years. There is a significant increase in frequency and extremity of meteorological and hydrological events (EEA, 2007) that lead to distinct excess or lack of water in landscape. These phenomena affect not only actual quantity of water but also its quality with direct and indirect impacts on aquatic organisms. From the environmental impact point of view, drought events are considered to be more dangerous due to their medium-term to long-term characteristics and large spatial impacts. However, this study presents that the particular flood event had significantly greater impact on water quality than the period of drought even if for only a very short time The paper reviews changes in water quality with all its consequences during selected extreme hydrological situations in the Czech Republic in last 10 years and compares them with the knowledge of impacts of floods and droughts on water quality collected from literature.     

Electronic States and Light Absorption in a Cylindrical Quantum Dot Having Thin Falciform Cross Section

Energy level structure and direct light absorption in a cylindrical quantum dot (CQD), having thin falciform cross section, are studied within the framework of the adiabatic approximation. An analytical expression for the energy spectrum of the particle is obtained. For the one-dimensional “fast” subsystem, an oscillatory dependence of the wave function amplitude on the cross section parameters is revealed. For treatment of the “slow” subsystem, parabolic and modified Pöschl-Teller effective potentials are used. It is shown that the low-energy levels of the spectrum are equidistant. In the strong quantization regime, the absorption coefficient and edge frequencies are calculated. Selection rules for the corresponding quantum transitions are obtained.     

Biomodification of fats and oils: Trials withCandida lipolytica

Various oil-accumulating yeasts were tested for their ability to produce lipase and live on fats and oils as carbon sources. Of these,Candida lipolytica seemed most promising, and the possibility was explored of modifying fats and oils by fermenting them withC. lipolytica and extracting the modified oil deposited in the yeast cells. Oxygen was required for the growth of yeast on fats and oils, but unless the oxygen level was controlled at a low value after cell populations peaked, most of the substrate oil was converted to citrates rather than accumulating as oil. Oil accumulation byC. lipolytica from a corn oil substrate was slightly depressed by excess nitrogen in the medium. The yeasts were able to use about 18 g/l of oil in 72 hr. At substrate oil levels greater than 18 g/l, the dry yeasts were 60% oil, and about 45–57% of the substrate oil was recovered as yeast oil. The fatty acid composition of the yeast oil was quite similar to that of the substrate oil under optimum conditions of deposition. Sterols, but not tocopherols, were transferred from the substrate to the yeast oil.Candida lipolytica oil was high in free fatty acids. The greatest potential for biomodification by fermentation withC. lipolytica seems to be in altering glyceride structure. Journal Paper No. J-11337 of the Iowa Agriculture and Home Economics Experiment Station, Ames, Project No. 2493.     

Crash costs by body part injured, fracture involvement, and threat-to-life severity. United States, 2000

This paper presents costs per US motor vehicle crash victim differentiated into many more diagnostic categories than prior estimates. These unit costs, which include the first keyed to the 1990 edition of Abbreviated Injury Scale (AIS) threat-to-life severity scores, are reported by body part, whether a fracture/dislocation was involved, and the maximum AIS score among the victim's injuries. This level of detail allows for a more accurate estimation of the social costs of motor vehicle crashes. It also allows for reliable analyses of interventions targeting narrow ranges of injuries. The paper updates the medical care data underlying the US crash costs from 1979 to 1986 to the mid 1990s and improves on prior productivity cost estimates. In addition to presenting the latest generation of crash victim costs, this paper analyzes the effects of applying injury costs classified by AIS code from the 1985 edition to injury incidence data coded with the 1990 edition of AIS. This long-standing practice results in inaccurate cost-benefit analyses that typically overestimate benefits. This problem is more acute when old published costs adjusted for inflation are used rather than the recent costs.     

Doping-induced broadening of the hole density-of-states in conducting polymers

The density-of-states distribution in conducting polymers reflects the energy disorder caused by electrostatic and steric interactions resulting from the different environment in which each molecule is placed. In case of p-doping (oxidation), the highest occupied molecular orbital (HOMO) manifold spreads in energy following a distribution as a result of long-range electrostatic (dipolar) interactions with the surrounding disordered host. In this paper the repercussion of the dipolar disorder on electrochemical signals of standard polypyrrole films is explored. The analysis is based on the chemical capacitance variation with the applied potential in experiments performed in quasi-equilibrium conditions. In addition to the Gaussian shape of cyclic voltammograms at low-doping levels, the model is able to qualitatively account for the current plateau usually observed at high oxidation potentials. This approach allows to estimating the dipolar moment associated to the polymer/dopant complex.