Heterogeneous Palladium Catalysts Applied to the Synthesis of 2‐ and 2,3‐Functionalised Indoles

Heterogeneous palladium catalysts ([Pd(NH₃)₄]²⁺/NaY and [Pd]/SBA‐15) were applied to the synthesis of 2‐functionalised indoles, giving generally high conversions and selectivities (>89% yield) using only 1 mol % [Pd]‐catalyst under standard reaction conditions (polar solvent, 80 °C). For the synthesis of 2,3‐functionalised indoles by cross‐coupling arylation, the [Pd]/SBA‐15 catalyst was found to be particularly interesting, producing the expected compound with =35% yield after 12 days of reaction, which is comparable to the homogeneous catalyst, Pd(OAc)₂ (=48% yield). In the course of the study, the dual reactivity of the indole nucleus was demonstrated: aryl bromides gave clean C C coupling while aryl iodides led to a clean C N coupling.     

Mature macrophage cell lines exhibit variable responses to LPS

Bacterial lipopolysaccharide (LPS) is a potent activator of cells of the macrophage/monocyte lineage. Two mature macrophage cell lines, P388D1 and RAW264.7, exhibit very different biological responses to LPS. Although RAW264.7 cells release arachidonic acid from phospholipid in response to LPS stimulation, P388D1 cells do not respond in this manner. However, LPS primes P388D1 cells to release arachidonic acid in response to other stimuli. The goal of this work is to contrast the biochemical events that occur in LPS-treated P388D1 and RAW264.7 macrophages. Enzyme assays indicate that LPS treatment induces the activation of cytosolic PLA2 in RAW264.7, but not in P388D1 cells. Phorbol ester (PMA), a receptor-independent stimulus, also fails to induce arachidonic acid release from P388D1 cells, suggesting that these cells may have a defect in the signal transduction machinery that is common to LPS and PMA. This hypothesis is supported by the observation that the expression of the LPS receptors CD14 and CD11b/CD18 is similar on P388D1 and RAW264.7 cells. Western blot analyses indicate that the erk kinases are activated upon LPS treatment of RAW264.7 but not P388D1 cells. LPS-induced arachidonic acid release is reduced in cells treated with the MEK inhibitor PD98059, suggesting that activated erk kinases mediate the phosphorylation and activation of cPLA2 in this system. Interestingly, the p42 isoform of erk (erk2) appears to be activated in resting P388D1 cells. This observation indicates that the MAP kinase cascade may be constitutively activated in P388D1 cells which may in turn limit their ability to respond to LPS. Together, these data provide evidence that mature macrophages from different sources can exhibit variable responses to LPS and highlight the danger of making generalizations regarding the effects of LPS on macrophages.     

FeS2 thin films prepared by spray pyrolysis

In the present work FeS₂ films have been grown by spray pyrolysis followed by sulfidation. The structural, optical and electrical properties of these films have been investigated. The films were found to be n-type with an indirect band gap of 1.17 eV. These films have a high potential for use in thin film solar cells and photoelectrochemical cells.     

Controlled growth of silicon nanowires on silicon surfaces

This paper reports on silicon nanowire growth on oxidized silicon substrates using different approaches for gold catalyst deposition. The gold coated surfaces and the resulting nanowires were characterized using scanning electron microscopy. The gold catalysts were made up of gold nanoparticles (50 nm diameter), which were either dispersed or spotted at different concentrations using a robot, or were formed on a patterned Si/SiO₂ substrate by metal evaporation (63 nm diameter). The subsequent silicon nanowire growth was accomplished by CVD decomposition of silane gas (SiH₄) at high temperature (400–500^°C) in a vapor-liquid-solid (VLS) process. Under these conditions, a high density of silicon nanowires (SiNWs) was achieved on the oxidized silicon surfaces, but the distribution of the nanowires was found to be inhomogeneous in the case of the gold nanoparticles. Such result is attributed to the aggregation of the nanoparticles during the growth process. Alternatively, when gold nanodot catalysts were lithographically patterned on the surface, the nanowires were obtained in the patterned regions.     

Crystalline ZnO and ZnO/TiO2 nanoparticles derived from tert-butyl N-(2 mercaptoethyl)carbamatozinc(II) chelate: Electrocatalytic studies for H2 generation in alkaline electrolytes

A newly synthesized zinc(II) complex, namely tert-butyl N-(2 mercaptoethyl)carbamatozinc(II) complex [Zn(Boc-S)₂] (Boc = tert-butyl N-[2-mercaptoethyl]carbamate), has been used as an organozinc precursor for the production of crystalline ZnO and ZnO/TiO₂ nanoparticles. The synthesized complex and the obtained nanomaterials were fully characterized using various spectroscopic and surface analysis techniques. Their surface morphology, chemical purity and stoichiometry have been investigated by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) as well as X-ray fluorescence. The synthesized Zn(II) molecular complex, ZnO and ZnO/TiO₂ nanomaterials have been tested in alkaline aqueous solution (1.0 MNaOH) for the hydrogen evolution reaction (HER) using various electrochemical techniques. The results revealed high HER catalytic performance of ZnO and ZnO/TiO₂ cathode materials, with the latter exhibiting higher catalytic activity recording an exchange current density (j_o) of 0.3 mA cm⁻². This current value, which approaches that of Pt wire (0.5 mA cm⁻²), cross-sectional area ~0.008 cm², is about 11 and 100 times greater than those measured for ZnO alone (0.028 mA cm⁻²) and TiO₂ alone (0.0032 mA cm⁻²), respectively. Moderate catalytic activity was recorded for the complex catalyst, namely GC-Zn(Boc-S)₂ with j_o value of (0.01 mA cm⁻²). Tafel slope values of 130 and 122 mV dec⁻¹ were calculated for ZnO and ZnO/TiO₂, respectively. Such Tafel slope values, which are close to that of the Pt wire (120 mV dec⁻¹), referred to a Volmer-controlled HER kinetics. Other important electrochemical parameters describing the kinetics of the HER, such as roughness factor (R_f) and turnover frequency (TOF) were also estimated and discussed. The high numerical values of the various HER kinetic parameters recorded for the ZnO/TiO₂ catalyst, in addition to its high stability and durability (stable for up to 10 000 continuous cathodic polarization cycles), besides maintaining its morphology and chemical composition after stability test (confirmed from SEM/EDX and XRD examinations), located it in a privileged position among the most efficient HER electrocatalysts reported in the literature.     

Electrosynthesis and analysis of the electrochemical properties of a composite material: Polyaniline + titanium oxide

The analysis of the electrochemical and spectroscopic properties of a composite material obtained starting from the polyaniline and TiO₂ in H₂SO₄ medium, using cyclic voltamperometry, shows three redox couples characteristic of the different oxidation and reduction states of produced polymer. The electroactivity of the composite in acid medium was better than that obtained in basic medium. The impedance spectroscopy study shows that the resistance of the film increases with the aniline concentration, but is not significantly affected by the amount of TiO₂ incorporated in polymer. The increase of pH decreases the resistance of the films and consequently increases its conductivity.     

Gold island films on indium tin oxide for localized surface plasmon sensing

Mechanically, chemically and optically stable gold island films were prepared on indium tin oxide (ITO) substrates by direct thermal evaporation of thin gold films (2-6?nm) without the need for pre-?or post-coating. The effect of mild thermal annealing (150?°C, 12?h) or short high temperature annealing (500?°C, 1?min) on the morphology of the gold nanostructures was investigated. ITO covered with 2?nm gold nanoislands and annealed at 500?°C for 1?min was investigated for its ability to detect the adsorption of biotinylated bovine serum albumin using local surface plasmon resonance (LSPR), and its subsequent molecular recognition of avidin.     

Computer Aided Diagnosis of Melanoma Using Deep Neural Networks and Game Theory: Application on Dermoscopic Images of Skin Lesions

Early detection of melanoma remains a daily challenge due to the increasing number of cases and the lack of dermatologists. Thus, AI-assisted diagnosis is considered as a possible solution for this issue. Despite the great advances brought by deep learning and especially convolutional neural networks (CNNs), computer-aided diagnosis (CAD) systems are still not used in clinical practice. This may be explained by the dermatologist’s fear of being misled by a false negative and the assimilation of CNNs to a “black box”, making their decision process difficult to understand by a non-expert. Decision theory, especially game theory, is a potential solution as it focuses on identifying the best decision option that maximizes the decision-maker’s expected utility. This study presents a new framework for automated melanoma diagnosis. Pursuing the goal of improving the performance of existing systems, our approach also attempts to bring more transparency in the decision process. The proposed framework includes a multi-class CNN and six binary CNNs assimilated to players. The players’ strategies is to first cluster the pigmented lesions (melanoma, nevus, and benign keratosis), using the introduced method of evaluating the confidence of the predictions, into confidence level (confident, medium, uncertain). Then, a subset of players has the strategy to refine the diagnosis for difficult lesions with medium and uncertain prediction. We used EfficientNetB5 as the backbone of our networks and evaluated our approach on the public ISIC dataset consisting of 8917 lesions: melanoma (1113), nevi (6705) and benign keratosis (1099). The proposed framework achieved an area under the receiver operating curve (AUROC) of 0.93 for melanoma, 0.96 for nevus and 0.97 for benign keratosis. Furthermore, our approach outperformed existing methods in this task, improving the balanced accuracy (BACC) of the best compared method from 77% to 86%. These results suggest that our framework provides an effective and explainable decision-making strategy. This approach could help dermatologists in their clinical practice for patients with atypical and difficult-to-diagnose pigmented lesions. We also believe that our system could serve as a didactic tool for less experienced dermatologists.     

Effect of Both Sn Doping and Annealing Temperature on the Properties of Dip-Coated Nanostructured TiO2 Thin Films

Journal of Inorganic and Organometallic Polymers and Materials - The synthesis of active thin films supported on substrates overcomes the drawbacks of powder-based photocatalysis and energy...     

Joint channel estimation and data detection for high rate orthogonal time frequency space systems

This paper proposes a new pilot pattern in the delay-Doppler (DD) domain for the orthogonal time frequency space (OTFS) system. In contrast to the embedded-pilot schemes, guard intervals are not used so as increase the spectral efficiency. Also, compared to the superimposed design where data symbols and pilots are arranged on the entire DD grid, in the proposed rearrangement, the number of pilots used is only spread over a subgrid of the DD grid. Hence, the interference of pilots with data symbols is reduced. Afterwards, an algorithm for channel estimation (CE) and symbol detection in the DD domain benefiting from the sparsity of the DD channel is designed. The sparse CE step is formulated as a specific marginalization of the maximum a posteriori (MAP) criterion by providing a Bayesian approach via the mean-field approximation that involves the variational Bayesian expectation maximization (VB-EM) algorithm. Detection of data symbols is done using a low complexity MP algorithm. We also propose an interference cancellation (IC) scheme to mitigate contamination of data by pilots that is run after each CE step. To achieve a high CE accuracy, based on the mean mutual incoherence property (MIP), a pilot optimization problem for OTFS is formulated and develop a simulated annealing-based algorithm to solve it. Finally, simulation results show that the proposed scheme achieves a good compromise between spectral efficiency, complexity, and performance in terms of bit error rate (BER) and normalized mean square error (NMSE) when compared to literature benchmarks.