Fully-Naphthalenoid Hydrocarbons and their Conjugation Modes

Abstract

A fully-naphthalenoid hydrocarbon (FUN) is a benzenoid hydrocarbon whose all π-electrons can be (formally) grouped into disjoint naphthalene-units. The cyclic conjugation in FUNs is studied by means of the energy-effects of their various cycles. It is found that the dominant conjugation modes in FUNs are those involving the 6- and 10-membered cycles of the “full” naphthalene fragments. The cycles belonging to the “empty” domains of a FUN have significantly smaller energy-effects.     

Influence of shear flow on the preparation of polymer layered silicate nanocomposites

In this paper the influence of melt-processing on the final polymer/layered silicate nanocomposite morphology is discussed. In particular the role of shear forces on the transformation of the original large clay agglomerates is of interest. Several polymer nanocomposites were prepared by melt-extrusion, involving polycaprolactone, poly(ethylene oxide), polyamide-12 or polyamide-6 as the matrix polymer. The nanocomposite morphology was characterised by X-ray diffraction and transmission electron microscopy and the clay tactoid morphology with polarised optical microscopy and scanning electron microscopy. The development of the tactoid and nanocomposite morphology during melt-mixing under shear was studied time-resolved by optical microscopy in conjunction with a rheometer and synchrotron X-ray scattering together with a Couette type flow cell. The shear forces in the melt-preparation of polymer layered mineral nanocomposites facilitate the break-up of large-sized agglomerates, whereas the extent of further exfoliation of the mineral layers is determined by the compatibility between the polymer matrix and the mineral layers rather than by shear forces.     

Effect of grass vs. concentrate feeding on the fatty acid profile of different fat depots in lambs

The aim of this study was to produce high‐quality meat from lambs under different feeding conditions, as measured by the accumulation of n‐3 fatty acids and conjugated linoleic acids (CLA) in muscle and subcutaneous fat. In total, 13 male crossbred lambs (Black Head×Gotland), each at 24 kg live weight, were divided into two feeding groups. Lambs were kept either on pasture (pasture grazing, n = 6) or in the stable (concentrate feeding, n = 7). The linolenic acid (C18:3n‐3) contained in the grass was absorbed and deposited into the different lipid classes of muscle and subcutaneous fat. The proportion of total n‐3 fatty acids in the different lipids of grazing lambs was significantly (p = 0.05) higher compared to that in concentrate‐fed lambs. The n‐6/n‐3 ratio (mean ± SEM) in muscle of grazing lambs was 1.2 ± 0.09 in contrast to 2.3 ± 0.09 (p = 0.05) of the animals kept in the stable. In subcutaneous fat, this ratio was 0.9 ± 0.2 in lambs kept on pasture versus 3.5 ± 0.2 (p = 0.05) after indoor keeping. The relative concentration of C18:1trans‐11 in total muscle lipids, phospholipids, triacylglycerols and subcutaneous fat was significantly increased by grass feeding compared to concentrate feeding. Significant influences of feeding were shown for saturated fatty acids. In concentrate‐fed lambs, a lower content of saturated fatty acids was detected. The proportion of CLAcis‐9,trans‐11 (1.9 ± 0.2% vs. 1.1 ± 0.1% in muscle, 2.5 ± 0.2% vs. 1.4 ± 0.2% in subcutaneous fat, 0.7 ± 0.04% vs. 0.4 ± 0.04% in phospholipids) in lambs was significantly (p = 0.05) higher after grazing than after concentrate feeding, respectively.     

Borcalein: a Carborane-Based Analogue of Baicalein with 12-Lipoxygenase-Independent Toxicity

12-Lipoxygenase is crucial for tumour angiogenesis. 5,6,7-Trihydroxy-2-phenyl-4H-1-benzopyran-4-one (baicalein) is a suitable inhibitor for this enzyme but is rapidly metabolised in vivo. Thus, an improvement of the metabolic stability is necessary to enhance the therapeutic efficiency. An emerging approach to enhance metabolic stability of carbon-based pharmaceuticals is the use of metabolically stable, non-toxic boron clusters, such as dicarba-closo-dodecaborane(12)s (carboranes) as phenyl mimetics. Therefore, the unsubstituted phenyl ring of baicalein was replaced by meta-carborane, resulting in borcalein, the carborane analogue of baicalein. This substitution resulted in a decreased inhibitory activity toward 12-lipoxygenase, but led to increased toxicity in melanoma (A375, B16, B16F10) and colon cancer cell lines (SW480, HCT116, CT26CL25) with decreased tumour selectivity in comparison to baicalein. Surprisingly, borcalein displays a different mechanism of cytotoxicity with increased intracellular production of reactive oxygen species (ROS), reactive nitrogen species (RNS) and nitric oxide (NO).     

Structure-Activity Relationships for 5′′ Modifications of 4,5-Aminoglycoside Antibiotics

Modification at the 5’’-position of 4,5-disubstituted aminoglycoside antibiotics (AGAs) to circumvent inactivation by aminoglycoside modifying enzymes (AMEs) is well known. Such modifications, however, unpredictably impact activity and affect target selectivity thereby hindering drug development. A survey of 5’’-modifications of the 4,5-AGAs and the related 5-O-furanosyl apramycin derivatives is presented. In the neomycin and the apralog series, all modifications were well-tolerated, but other 4,5-AGAs require a hydrogen bonding group at the 5’’-position for maintenance of antibacterial activity. The 5’’-amino modification resulted in parent-like activity, but reduced selectivity against the human cytosolic decoding A site rendering this modification unfavorable in paromomycin, propylamycin, and ribostamycin. Installation of a 5’’-formamido group and, to a lesser degree, a 5’’-ureido group resulted in parent-like activity without loss of selectivity. These lessons will aid the design of next-generation AGAs capable of circumventing AME action while maintaining high antibacterial activity and target selectivity.     

Reduction of NOx by H2 on WOx-Promoted Pt/Al2O3/SiO2 Catalysts Under O2-Rich Conditions

This work addresses the reduction of NO_x by H₂ under O₂-rich conditions using Al₂O₃/SiO₂-supported Pt catalysts with different loads of WO_x promotor. The samples were thoroughly characterised by N₂ physisorption, temperature-programmed desorption of CO, scanning electron microscopy, X-ray diffraction, laser raman spectroscopy, X-ray photoelectron spectroscopy and diffuse reflectance infrared fourier transform spectroscopy with probe molecule CO. The catalytic studies of the samples without WO_x showed pronounced NO_x conversion below 200 °C, whereas highest efficiency was related to small Pt particles. The introduction of WO_x provided increasing deNO_x activity as well as N₂ selectivity. This promoting effect was referred to an additional reaction path at the Pt-WO_x/Al₂O₃/SiO₂ interface, whereas an electronic activation of Pt by strong metal support interaction was excluded.

Graphic Abstract

     

On-line monitoring of fuel moisture-content in biomass-fired furnaces by measuring relative humidity of the flue gases

Combustion of biomass for heat and power production is continuously growing in importance, because of incentives for replacing fossil energy resources with renewable ones. In biomass combustion, the moisture content of the fuel is an essential operation parameter, which often fluctuates for biomass fuels. Variation in moisture content complicates the operation of the furnaces and results in an uncertainty in the energy content of the fuel delivered to a plant. The fuel moisture-content in a furnace may be determined either by direct measurement on the entering fuel or by measuring the moisture and oxygen contents of the flue gases deriving the moisture content of the fuel. However, reliable methods of a motivated cost for the small to medium-scale furnaces are today not available. An exception is if the furnace is equipped with flue-gas condenser, which can be used to estimate the moisture content of the flue gases. A limitation of this method is, though, that not all furnaces have flue-gas condensers and that the measured signal has an inherent time delay.In this work, measurement of the relative humidity (RH) of the flue gases from a furnace is investigated as the central component in the on-line monitoring of the moisture content of the fuel in a furnace. The method was analysed with humid air in a laboratory environment and tested for accuracy and dynamical behaviour in two biomass-fired heat-production units, one circulating fluidised-bed boiler (CFB) and one grate furnace. The results show that the method, which is easy to calibrate on site, can be used to predict the moisture content of the biomass fuel in the grate furnace with very good precision (<4% error). Furthermore, the method detects variations in moisture content of the furnace flue gases due to changes in the moisture content of the combusted fuel within the order of seconds. Since the transport time of the flue gases from the furnace to the measurement position is of the same order of magnitude, the total time for detection of a change in the moisture content of the fuel is small enough for the signal to be used to control both the fuel feed and the combustion air in a grate furnace.     

Effective reduction of AlN defect luminescence by fluorine implantation

We report on the effective reduction of AlN host lattice defect cathodoluminescence by high dose ion implantation of light elements such as fluorine as well as chlorine and neon with peak concentrations of 1 at.%. In order to distinguish between luminescence suppression in the visible to luminescence quenching due to radiation damage, all samples were additionally implanted with europium at fluences of 1 · 10¹³ ions/cm². After annealing the samples at 1373 K under vacuum conditions cathodoluminescence spectra were recorded at room temperature (300 K) and at cryogenic temperature (12 K). These investigations reveal that different light ion species have different influences on the defect luminescence of the AlN host lattice which is likely due to selective passivation of these defects. The best ratio of defect luminescence suppression to radiation damage induced luminescence quenching is achieved in the case of fluorine co-doping.     

The Adhesion‐Enhanced Contact Electrification and Efficiency of Triboelectric Nanogenerators

In the present work, the contact electrification of polymers that differ in adhesion strength is studied. Electrical current is measured along with adhesion in macroscale contacting‐separation experiments. Additionally, local adhesion and roughness are studied with atomic force microscopy to get deeper insight into relations between surface properties and electrification. Measurements reveal that higher surface charge is formed on more adhesive surfaces, thus confirming covalent bond cleavage as a mechanism for contact electrification of polymers. Investigated materials possess enhanced contact electrification making them attractive candidates for the conversion of mechanical energy to electrical in triboelectric nanogenerator devices.     

Modeling Alcohol Dehydrogenase Catalysis in Deep Eutectic Solvent/Water Mixtures

The use of oxidoreductases (EC1) in non-conventional reaction media has been increasingly explored. In particular, deep eutectic solvents (DESs) have emerged as a novel class of solvents. Herein, an in-depth study of bioreduction with an alcohol dehydrogenase (ADH) in the DES glyceline is presented. The activity and stability of ADH in mixtures of glyceline/water with varying water contents were measured. Furthermore, the thermodynamic water activity and viscosity of mixtures of glyceline/water have been determined. For a better understanding of the observations, molecular dynamics simulations were performed to quantify the molecular flexibility, hydration layer, and intraprotein hydrogen bonds of ADH. The behavior of the enzyme in DESs follows the classic dependence of water activity (a_W) in non-conventional media. At low a_W values (<0.2), ADH does not show any activity; at higher a_W values, the activity was still lower than that in pure water due to the high viscosities of the DES. These findings could be further explained by increased enzyme flexibility with increasing water content.