Simultaneous oxidation of aromatic compounds using Sr-doped lanthanum manganites as catalysts

Strontium-doped lanthanum manganites, La_1-xSr_xMnO₃ (LSMO), are promising and affordable catalysts for oxidative degradation of volatile organic compounds. LSMO catalysts (x = 0, .1, .2, and .3) were prepared by the citrate-nitrate autocombustion (CNA) and coprecipitation synthesis. The phase composition was confirmed by X-ray diffraction and Rietveld refinement analysis, while the oxygen content was determined by Mohr's salt permanganate titration. Morphology and porosity of prepared catalysts was correlated to catalytic oxidation of benzene, toluene, ethylbenzene and o-xylene. It was observed that both synthesis methods yielded catalysts of similar average pore size diameter and specific surface area, but the pore size distribution differed: CNA-prepared catalysts had a multimodal pore size distribution, while the coprecipitated ones had a single maximum at 4 nm. Catalysts prepared by the CNA method have shown a higher catalytic activity in the temperature range 373–723 K, as the presence of Mn³⁺/Mn⁴⁺ mixed valences increased their reducibility.     

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).     

Anticancer Potential of (Pentamethylcyclopentadienyl)chloridoiridium(III) Complexes Bearing κP and κP,κS‐Coordinated Ph2PCH2CH2CH2S(O)xPh (x=0–2) Ligands

Iridium(III) complexes of the type [Ir(η⁵‐C₅Me₅)Cl₂{Ph₂PCH₂CH₂CH₂S(O)_xPh‐κP}] (x=0–2; 1 – 3 ) and [Ir(η⁵‐C₅Me₅)Cl{Ph₂PCH₂CH₂CH₂S(O)_xPh‐κP,κS}][PF₆] (x=0–1; 4 and 5 ) with 3‐(diphenylphosphino)propyl phenyl sulfide, sulfoxide, and sulfone ligands Ph₂PCH₂CH₂CH₂S(O)_xPh were designed, synthesized, and characterized fully, including X‐ray diffraction analyses for complexes 3 and 4 . In vitro studies against human thyroid carcinoma (8505C), submandibular carcinoma (A253), breast adenocarcinoma (MCF‐7), colon adenocarcinoma (SW480), and melanoma (518A2) cell lines provided evidence for the high biological potential of the neutral and cationic iridium(III) complexes. Neutral iridium(III) complex 5 proved to be the most active, with IC₅₀ values up to about 0.1 μM , representing activities of up to one order of magnitude higher than cisplatin. Using 8505C cells, apoptosis was shown to be the main mechanism through which complex 5 exerts its tumoricidal action. The described iridium(III) complexes represent potential leads in the search for novel metal‐based anticancer agents.     

MALDI-TOF MS and Morphology Studies of Thiacalixarene-Silsesquioxane Products of Oligo- and Polycondensation

For the first time condensed silsesquioxane derivatives of tetratrialkoxysilyl compounds have been characterized by MALDI-TOF mass spectrometry. Tetrasubstituted p-tert-butyl thiacalix[4]arene derivatives containing organosilicon fragments with variable stereochemistry were chosen as organosilicon compounds for polycondensation. Information obtained from mass spectra was used to deduce both the structures of oligomeric derivatives, as well as the structure of silsesquioxane framework. The morphology of formed polysilsesquioxanes was investigated by scanning and transmission electron microscopy.     

Photoluminescence decay rate of silicon nanoparticles modified with gold nanoislands

We investigated plasmon-assisted enhancement of emission from silicon nanoparticles (ncs-Si) embedded into porous SiO _x matrix in the 500- to 820-nm wavelength range. In the presence in the near-surface region of gold nanoisland film, ncs-Si exhibited up to twofold luminescence enhancement at emission frequencies that correspond to the plasmon resonance frequency of Au nanoparticles. Enhancement of the photoluminescence (PL) intensity was attributed to coupling with the localized surface plasmons (LSPs) excited in Au nanoparticles and to increase in the radiative decay rate of ncs-Si. It has been shown that spontaneous emission decay rate of ncs-Si modified by thin Au film over the wide emission spectral range was accelerated. The emission decay rate distribution was determined by fitting the experimental decay curves to the stretched exponential model. The observed increase of the PL decay rate distribution width for the Au-coated nc-Si-SiO _x sample in comparison with the uncoated one was explained by fluctuations in the surface-plasmon excitation rate.

PACS

78. 67. Bf; 78.55.-m     

Visualization of the Centre of Projection Geometrical Locus in a Single Image

Single view reconstruction (SVR) is an important approach for 3D shape recovery since many non‐existing buildings and scenes are captured in a single image. Historical photographs are often the most precise source for virtual reconstruction of a damaged cultural heritage. In semi‐automated techniques, that are mainly used under practical situations, the user is the one who recognizes and selects constraints to be used. Hence, the veridicality and the accuracy of the final model partially rely on man‐based decisions. We noticed that users, especially non‐expert users such as cultural heritage professionals, usually do not fully understand the SVR process, which is why they have trouble in decision making while modelling. That often fundamentally affects the quality of the final 3D models. Considering the importance of human performance in SVR approaches, in this paper we offer a solution that can be used to reduce the amount of user errors. Specifically, we address the problem of locating the centre of projection (CP). We introduce a tool set for 3D visualization of the CP's geometrical loci that provides the user with a clear idea of how the CP's location is determined. Thanks to this type of visualization, the user becomes aware of the following: (1) the constraint relevant for CP location, (2) the image suitable for SVR, (3) more constraints for CP location required, (4) which constraints should be used for the best match, (5) will additional constraints create a useful redundancy. In order to test our approach and the assumptions it relies on, we compared the amount of user made errors in the standard approaches with the one in which additional visualization is provided.     

Detecting and tracking mesoscale precipitating objects using machine learning algorithms

Accurate identification of precipitating clouds is a challenging task. In the present work, Support Vector Machines (SVMs), Decision Trees (DT), and Random Forests (RD) algorithms were applied to extract and track mesoscale convective precipitating clouds from a series of 22 Geostationary Operational Environmental Satellite-13 meteorological image sub-scenes over the continental territory of Colombia. This study’s aims are twofold: (i) to establish whether the use of five meteorological spectral channels, rather than a single infrared (IR) channel, improves rainfall objects detection and (ii) to evaluate the potential of machine learning algorithms to locate precipitation clouds. Results show that while the SVM algorithm provides more accurate classification of rainfall cloud objects than the traditional IR brightness temperature threshold method, such improvement is not statistically significant. Accuracy assessment was performed using STEP (shape (S), theme (T), edge (E), and position (P)) object-based similarity matrix method, taking as reference precipitation satellite images from the Tropical Rainfall Measuring Mission. Best thematic and geometric accuracies were obtained applying the SVM algorithm.     

The influence of spiral jet-milling on the physicochemical properties of carbamazepine form III crystals: Quality by design approach

The purpose of this study was to investigate the influence of spiral jet-milling process on the physicochemical characteristics of α polymorphic active pharmaceutical ingredient, using Carbamazepine form III as a model drug, and taking into consideration Quality by Design (QbD) approach to pharmaceutical development. A 2^(4-1) factorial screening design was implemented to identify the spiral jet-milling process variables that significantly affect the particle size distribution of milled samples. Diameter of injector nozzles, diameter of ring nozzles and air pressure were selected for further analysis using a 2^(3-1) factorial experimental design. Particle size distribution of additional samples was determined, while physicochemical properties were examined by differential scanning calorimetry (DSC), hot-stage polarized microscopy (HSPM), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), and compared to those of un-milled drug. The gathered results shown that applied experimental design approach is capable to predict material behavior and could help in better understanding of material behavior during jet-milling process. Created design space (DS) provides assurance of product quality, expressed as the powder particle sizes lower than 5 μm, as well as, in initial polymorph form existence after jet-milling through combination and interaction of input variables.     

The kinetic and thermodynamic analysis of ultrasound-extraction of minerals from aerial parts of white lady's bedstraw (Galium mollugo L.)

The present paper deals with the extraction of some minerals (potassium, calcium and magnesium) from ground, dried aerial parts of white lady's bedstraw (Galium mollugo L.) using an aqueous ethanol solution (50% by volume) at different temperatures (from 23 to 40 °C) in the presence and absence of ultrasound. The main goal was to establish the kinetics and the thermodynamics of the two extraction processes. A phenomenological model involving simultaneous washing and diffusion was proved for both ultrasound-assisted and silent extraction of the minerals. The minerals extraction both in the presence and the absence of ultrasound is endothermic and irreversible since the enthalpy change and the entropy change are positive in the ranges of extraction temperature applied. The Gibbs free energy change for the extraction of minerals is negative, indicating that the process is feasible and spontaneous. The minerals yield increased by a factor of 1.02–1.06 and 1.14–1.27 in the absence and the presence of ultrasound, respectively for every 10 °C rise in temperature.