Nonisothermal decomposition kinetics of [CoC<Subscript>2</Subscript>O<Subscript>4</Subscript>·2.5H<Subscript>2</Subscript>O]<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>

The authors present their results concerning the decomposition in air of the homopolynuclear coordination compound [CoC₂O₄·2.5H₂O] _n . In the temperature range 20–300 °C, the heating curves TG, DTG and DTA allowed to evidence three decomposition steps. The kinetic analysis was performed on the second step which proved to be the only workable one. The application of nonlinear regression procedure shows that this is a complex process consisting in three successive steps. The checking of the mechanism and corresponding kinetic parameters for quasi-isothermal data (T = 150 °C) shows that the obtained results could be used for prediction of the thermal behaviour of the investigated compound in both isothermal and non-isothermal conditions.     

Quantifying seismic survey reverberation off the Alaskan North Slope

Shallow-water airgun survey activities off the North Slope of Alaska generate impulsive sounds that are the focus of much regulatory attention. Reverberation from repetitive airgun shots, however, can also increase background noise levels, which can decrease the detection range of nearby passive acoustic monitoring (PAM) systems. Typical acoustic metrics for impulsive signals provide no quantitative information about reverberation or its relative effect on the ambient acoustic environment. Here, two conservative metrics are defined for quantifying reverberation: a minimum level metric measures reverberation levels that exist between airgun pulse arrivals, while a reverberation metric estimates the relative magnitude of reverberation vs expected ambient levels in the hypothetical absence of airgun activity, using satellite-measured wind data. The metrics are applied to acoustic data measured by autonomous recorders in the Alaskan Beaufort Sea in 2008 and demonstrate how seismic surveys can increase the background noise over natural ambient levels by 30-45 dB within 1 km of the activity, by 10-25 dB within 15 km of the activity, and by a few dB at 128 km range. These results suggest that shallow-water reverberation would reduce the performance of nearby PAM systems when monitoring for marine mammals within a few kilometers of shallow-water seismic surveys.     

Studies on new hybrid materials prepared by both Diels–Alder and Michael addition reactions

New polyurethane chemically crosslinked networks containing silica were synthesized by both Diels–Alder polymerization and Michael addition reaction. Structural characterization of the products was evidenced by proton nuclear magnetic resonance and attenuated total reflectance in conjunction with Fourier transform infrared spectroscopy techniques. Differential scanning calorimetry was used to demonstrate the thermally remendable character of the materials obtained through Diels–Alder polymerization. The influence of increasing silica content on the glass transition temperatures was studied. It was observed that the glass transition temperatures increased with increasing silica content. Absolute heat capacities and crosslinking densities were determined for the thermoreversible materials. A comparison between materials obtained through Diels–Alder process and Michael addition method was studied. A kinetic study was conducted via an isoconversional method. Morphological studies were conducted by atomic force microscopy technique.     

Eco-Friendly Nitrogen-Doped Graphene Preparation and Design for the Oxygen Reduction Reaction

Four N-doped graphene materials with a nitrogen content ranging from 8.34 to 13.1 wt.% are prepared by the ball milling method. This method represents an eco-friendly mechanochemical process that can be easily adapted for industrial-scale productivity and allows both the exfoliation of graphite and the synthesis of large quantities of functionalized graphene. These materials are characterized by transmission and scanning electron microscopy, thermogravimetry measurements, X-ray powder diffraction, X-ray photoelectron and Raman spectroscopy, and then, are tested towards the oxygen reduction reaction by cyclic voltammetry and rotating disk electrode methods. Their responses towards ORR are analysed in correlation with their properties and use for the best ORR catalyst identification. However, even though the mechanochemical procedure and the characterization techniques are clean and green methods (i.e., water is the only solvent used for these syntheses and investigations), they are time consuming and, generally, a low number of materials can be prepared, characterized and tested. In order to eliminate some of these limitations, the use of regression learner and reverse engineering methods are proposed for facilitating the optimization of the synthesis conditions and the materials’ design. Thus, the machine learning algorithms are applied to data containing the synthesis parameters, the results obtained from different characterization techniques and the materials response towards ORR to quickly provide predictions that allow the best synthesis conditions or the best electrocatalysts’ identification.     

Synthesis and characterization of ZnO nanostructures obtained in mixtures of ionic liquids with organic solvents

ZnO nanoparticles were synthesized in mixtures of ionic liquids based on imidazolium cation with organic solvents (dimethyl sulfoxide and ethylene glycol) by a simple, one-step solution route at low temperature. The effect of these mixtures on the morphology, size and properties of as obtained ZnO nanopowders was investigated. The obtained nanopowders have been characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), UV-Vis absorption spectroscopy (UV-Vis) and photoluminescence (PL). The effect of the ionic liquid mixture on the photocatalytic degradation of methylene blue has been analysed. The XRD studies confirmed the hexagonal wurtzite structure of the obtained ZnO powder. The UV-Vis absorption spectra present the typical shape for ZnO, with a broad band situated in the UV region, with the maximum around 360 nm. The calculated band-gap energy is in interval 3.25–3.28 eV. The synthesized ZnO nanopowders have high photocatalytic activity against methylene blue, the best results being obtained when 1-ethyl-3-methylimidazolium tetrafluoroborate was used as the solvent.

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Chemical mapping of ceramide distribution in sphingomyelin-rich domains in monolayers

The incorporation of ceramide in phase-separated monolayers of ternary lipid mixtures has been studied by a combination of atomic force microscopy (AFM), fluorescence, and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Replacement of a fraction of the sphingomyelin by ceramide in DOPC/SM/cholesterol monolayers leads to changes in the SM-cholesterol-rich liquid-ordered domains. AFM shows the formation of heterogeneous domains with small raised islands that are assigned to a ceramide-rich gel phase. ToF-SIMS provides conclusive evidence for the localization of SM and ceramide in ordered domains and shows that ceramide is heterogeneously distributed in small islands throughout the domains. The results indicate the utility of combining AFM and ToF-SIMS for understanding compositions of phase-separated membranes.     

Synthesis and charge transport studies of stable, soluble hexacenes

Acenes larger than pentacene are predicted to possess enticing electronic properties, but are insoluble and prone to rapid decomposition. Utilizing a combination of functionalization strategies, we present stable, solution-processable hexacenes and an evaluation of their hole and electron transport properties.     

Design,synthesis and structure of new dendritic melamines. First use of a tandem C-2-substituted serinol—O,O-masked 4-piperidone as a peripheral unit in iterative synthesis

The iterative chemoselective amination of cyanuric chloride to dimers of new G-2 dendritic N-substituted-2,4,6-triamino-s-triazines (melamines) having C-2-substituted 2-aminopropane-1,3-diols (‘serinols’) in tandem with the ethylene ketal of 4-piperidone as peripheral units is reported. The structure as a function of increasing molecular size was studied by NMR spectroscopy, DFT calculation and AFM imaging. A concise nomenclature defining the restricted rotational phenomena about the newly created C(s-triazine)–N(exocyclic) partial double bonds, seen as axes of (pro)diastereomerism, is used. We propose a new form of frontier rotamerism for the dendrimer surface, which operates over a long range.     

DFT and TDDFT study related to electron transfer in nonbonded porphine...C60 complexes

Spectroscopic properties of a ground state nonbonded porphine-buckminsterfullerene (H2P...C60) complex are studied in several different relative orientations of C60 with respect to the porphine plane by using the density functional (DFT) and time-dependent density functional (TDDFT) theories. The geometries and electronic structures of the ground states are optimized with the B3LYP and PBE functionals and a SVP basis set. Excitation energies and oscillator strengths are obtained from the TDDFT calculations. The relative orientation of C60 is found to affect the equilibrium distance between H2P and C60 especially in the case of the PBE functional. The excitation energies of different H2P...C60 complexes are found to be practically the same for the same excitations when the B3LYP functional is used but to differ notably when PBE is used in calculations. Existence of the states related to a photoinduced electron transfer within a porphyrin-fullerene dyad is also studied. All calculations predict a formation of an excited charge-transfer complex state, a locally excited donor (porphine) state, as well as a locally excited acceptor (fullerene) state in the investigated H2P...C60 complexes.     

Spontaneous Formation of Giant Unilamellar Vesicles from Microdroplets of a Polyion Complex by Thermally Induced Phase Separation

Water pump : Polyion complex (PIC) vesicles are spontaneously formed from PIC microdroplets, which are formed by mixing cationic and anionic polymers (see picture). The formation process can be reversibly controlled by local heating with a focused infrared laser that triggers microphase separation and subsequent water influx. The size of the resulting giant unilamellar vesicles is determined by the initial size of the PIC droplets.