ALBERT

Description: A unique automated planetary boundary layer (PBL) retrieval algorithm is proposed as a common cross-platform method for use with commercially available ceilometers for implementation under the redesigned U.S. Environmental Protection Agency Photochemical Assessment Monitoring Stations program. This algorithm addresses instrument signal quality and screens for precipitation and cloud layers before the implementation of the retrieval methodology using the Haar wavelet covariance transform method. Layer attribution for the PBL height is supported with the use of continuation and time-tracking parameters, and uncertainties are calculated for individual PBL height retrievals. Commercial ceilometer retrievals are tested against radiosonde PBL height and cloud-base height during morning and late afternoon transition times, critical to air quality model prediction and when retrieval algorithms struggle to identify PBL heights. A total of 58 radiosonde profiles were used and retrievals for nocturnal stable layers, residual layers and mixing layers were assessed. Overall good agreement was found for all comparisons with one system showing limitations for the cases of nighttime surface stable layers and daytime mixing layer. It is recommended that nighttime shallow stable layer retrievals be performed with a recommended minimum height or with additional verification. Retrievals of residual layer heights and mixing layer comparisons revealed overall good correlations to radiosonde heights (correlation coefficients, r2, ranging from 0.89 – 0.96 and bias ranging from ~ -131 to +63 m, and r2 from 0.88 – 0.97 and bias from -119 to +101 m, respectively).

Description: Recently, it has been established that interplanetary coronal mass ejections (ICMEs) can dramatically affect both trapped electron fluxes in the outer radiation belt and precipitating electron fluxes lost from the belt into the atmosphere. Precipitating electron fluxes and energies can vary over a range of timescales during these events. These variations depend on the initial energy and location of the electron population and the ICME characteristics and structures. One important factor controlling electron dynamics is the magnetic field orientation within the ejecta that is an integral part of the ICME. In this study, we examine Van Allen Probes (RBSPs) and Polar Orbiting Environmental Satellites (POESs) data to explore trapped and precipitating electron fluxes during two ICMEs. The ejecta in the selected ICMEs have magnetic cloud characteristics that exhibit the opposite sense of the rotation of the north–south magnetic field component (BZ). RBSP data are used to study trapped electron fluxes in situ, while POES data are used for electron fluxes precipitating into the upper atmosphere. The trapped and precipitating electron fluxes are qualitatively analysed to understand their variation in relation to each other and to the magnetic cloud rotation during these events. Inner magnetospheric wave activity was also estimated using RBSP and Geostationary Operational Environmental Satellite (GOES) data. In each event, the largest changes in the location and magnitude of both the trapped and precipitating electron fluxes occurred during the southward portion of the magnetic cloud. Significant changes also occurred during the end of the sheath and at the sheath–ejecta boundary for the cloud with south to north magnetic field rotation, while the ICME with north to south rotation had significant changes at the end boundary of the cloud. The sense of rotation of BZ and its profile also clearly affects the coherence of the trapped and/or precipitating flux changes, timing of variations with respect to the ICME structures, and flux magnitude of different electron populations. The differing electron responses could therefore imply partly different dominant acceleration mechanisms acting on the outer radiation belt electron populations as a result of opposite magnetic cloud rotation.

Description: The terpenoid (−)-Istanbulin A is a natural product isolated from Senecio filaginoides DC, one of the 270 species of Senecio (Asteraceae) which occurs in Argentina. The structure and absolute configuration of this compound [9a-hydroxy-3,4a,5-trimethyl-4a,6,7,8a,9,9a-hexahydro-4H,5H-naphtho[2,3-b]-furan-2,8-dione or (4S,5R,8R,10S)-1-oxo-8β-hydroxy-10βH-eremophil-7(11)-en-12,8β-olide, C15H20O4] were determined by single-crystal X-ray diffraction studies. It proved to be a sesquiterpene lactone showing an eremophilanolide skeleton whose chirality is described as 4S,5R,8R,10S. Structural results were also in agreement with the one- and two-dimensional (1D and 2D) NMR and HR–ESI–MS data, and other complementary spectroscopic information. In addition, (−)-Istanbulin A is a polymorph of the previously reported form of (−)-Istanbulin A, form I; thus, the title compound is denoted form II or polymorph II. Structural data and a literature search allowed the chirality of Istanbulin A to be revisited. The antimicrobial and antifungal activities of (−)-Istanbulin A, form II, were evaluated in order to establish a reference for future comparisons and applications related to specific crystal forms of Istanbulins.

Description: Two conformational polymorphs of (N,N-dibutyldithiocarbamato-κ2 S,S′)[tris(3,5-diphenylpyrazol-1-yl-κN 2)hydroborato]cobalt(II), [Co(C45H34BN6)(C9H18NS2)] or [TpPh2Co(S2CNBu2)], 1, are accessible by recrystallization from dichloromethane–methanol to give orthorhombic polymorph 1a, while slow evaporation from acetonitrile produces triclinic polymorph 1b. The two polymorphs have been characterized by IR spectroscopy and single-crystal X-ray crystallography at 150 K. Polymorphs 1a and 1b crystallize in the orthorhombic space group Pbca and the triclinic space group P-1, respectively. The polymorphs have a trans (1a) and cis (1b) orientation of the butyl groups with respect to the S2CN plane of the dithiocarbamate ligand, which results in an intermediate five-coordinate geometry for 1a and a square-pyramidal geometry for 1b. Hirshfeld surface analysis reveals minor differences between the two polymorphs, with 1a exhibiting stronger C—H...S interactions and 1b favouring C—H...π interactions.

Description: In this study, the effect of thermo-mechanical densification on the density, hardness, compression strength, bending strength (MOR), and modulus of elasticity (MOE) of fir and aspen wood pretreated with water repellents was analyzed. Wood specimens were impregnated with paraffin, linseed oil and styrene after pre-vacuum treatment. Then, the impregnated wood specimens were densified with compression ratios of 20 and 40%, and at 120, 150 and 180 °C. The results indicated that the density, hardness and strength properties of the all densified specimens (untreated and impregnated) increased depending on the compression ratio and temperature. For all tested properties, higher increases were obtained in the paraffin and styrene pretreated specimens compared to untreated samples. However, the increase rates in linseed oil pretreated specimens were generally lower than untreated specimens. Regarding water repellents the most successful results in all tested properties were determined in styrene pretreated specimens. The density, hardness and strength properties of all specimens increased with the increase in compression ratio. On the other hand, the increase in the compression temperature negatively affects the properties of untreated and linseed oil pretreated specimens, while having a generally positive effect on the properties of paraffin pretreated specimens. However, all tested properties of styrene pretreated specimens have increased significantly due to the increase in compression temperature. The increasing strength properties of wood as a result of densification have increased much more with paraffin and especially styrene pretreatment. These combinations can be considered as an important potential for applications that require more hardness and strength.

Description: A supramolecular complex, formed by encapsulation of C60 fullerene in a molecular container built from two resorcin[4]arene rims zipped together by peptidic arms hydrogen bonded into a cylindrical β-sheet, was studied by X-ray crystallography, solid-state and solution NMR, EPR spectroscopy and differential scanning calorimetry (DSC). The crystal structure, determined at 100 K, reveals that the complex occupies 422 site symmetry, which is compatible with the molecular symmetry of the container but not of the fullerene molecule, which has only 222 symmetry. The additional crystallographic symmetry leads to a complicated but discrete disorder, which could be resolved and modelled using advanced features of the existing refinement software. Solid-state NMR measurements at 184–333 K indicate that the thermal motion of C60 in this temperature range is fast but has different activation energies at different temperatures, which was attributed to a phase transition, which was confirmed by DSC. Intriguingly, the activation energy for reorientations of C60 in the solid state is very similar for the free and encaged molecules. Also, the rotational diffusion coefficients seem to be very similar or even slightly higher for the encaged fullerene compared to the free molecule. We also found that chemical shift anisotropy (CSA) is not the main relaxation mechanism for the 13C spins of C60 in the studied complex.

Description: This study aims at identifying the mechanisms of oil and water imbibition in heartwood and sapwood of Douglas-fir through a combination of original experiments with magnetic resonance imaging (MRI) and nuclear magnetic resonance (NMR) relaxation measurements for oil and free water, and deformation measurements for bound water. Experiments by weighing are performed to verify whether the imbibition process is also consistent with Washburn law. All the results are discussed taking into account the structure of wood (tubular tracheids closed at their tips, but possibly connected to each other via open pits on the side faces) and the preparation of samples. The observation of relatively fast oil flow imbibition confirms that sapwood exhibits a connected hydraulic network through which a liquid can a priori flow and climb along the structure. However, the spontaneous water imbibition is strongly damped by its very poor wetting when in contact with cell-walls only partially saturated with bound water, so that the diffusion of bound water control the uptake dynamics. However, due to preferentially closed pits, the heartwood does not exhibit a continuous hydraulic network and water essentially penetrates into wood by diffusion through the cell walls.

Description: The objective of this work was to provide a rapid and nondestructive imaging method for evaluating the hygroscopic behavior of thermally modified lignocellulosic materials (softwood and hardwood). The difference in the hygroscopic behavior was explained by moisture content (MC) mapping results and molecular association characteristics of absorbed water (i.e. weakly, moderately, and strongly hydrogen-bonded water molecules) with wood at various relative humidities (RH). To achieve this goal, near-infrared (NIR) spectral images in the wavelength range 1816–2130 nm (covering the combination of stretching and deformation vibrations for OH) were used to visualize MC distributions over the surface of Japanese cedar and European beech samples which had been thermally treated at different temperatures. A curve fitting method was utilized to explore changes in water-wood structure characteristics based on shifts to longer wavelength in spectral signals caused by increasing MC. The curve fitting results support the recent nuclear magnetic resonance (NMR) studies that different bound water stabilities may pool in different compartments of the wood cell wall. Furthermore, water was firmly bound to wood at low RHs and H-bonds gained mobility as the number of absorbed molecules increased. It is concluded that NIR hyperspectral imaging also has the potential to be a complementary methodology for studying the transient changes of wood-water interactions before equilibrium.