Microwave-assisted synthesis and luminescent activity of imidazo[1,2-a]pyridine derivatives

In this work, a series of phenacyl bromide derivatives was synthesized and employed as key intermediate for the synthesis of substituted imidazo[1,2-a]pyridines. First, phenacyl bromide molecules were obtained from the bromination reaction of acetophenones assisted by microwave irradiation, obtaining the products 4a-v in a 15 minutes reaction with yields in the range of 50% to 99%. Subsequently, the conjugation of these molecules with 2-aminopyridine conduced to the production of imidazo[1,2-a]pyridine derivatives ( 7a-v ) in a 60-second reaction with yields of 24% to 99%. Improved yields were determined with respect to those obtained with more tedious methodologies like thermally and mechanically assisted routes. Intense luminescence emissions in the purple and blue regions of the electromagnetic spectra were observed under UV excitation according to the nature of the substituents. This environmentally friendly methodology is expected to constitute an important class of organic compounds for the development of biomarkers, photochemical sensors, and medicinal applications.     

Well-balanced unstaggered central schemes for one and two-dimensional shallow water equation systems

We propose a new well-balanced unstaggered central finite volume scheme for hyperbolic balance laws with geometrical source terms. In particular we construct a new one and two-dimensional finite volume method for the numerical solution of shallow water equations on flat/variable bottom topographies. The proposed scheme evolves a non-oscillatory numerical solution on a single grid, avoids the time consuming process of solving Riemann problems arising at the cell interfaces, and is second-order accurate both in space and time. Furthermore, the numerical scheme follows a well-balanced discretization that first discretizes the geometrical source term according to the discretization of the flux terms, and then mimics the surface gradient method and discretizes the water height according to the discretization of the water level. The resulting scheme exactly satisfies the C-property at the discrete level. The proposed scheme is then applied and classical one and two-dimensional shallow water equation problems with flat or variable bottom topographies are successfully solved. The obtained numerical results are in good agreement with corresponding ones appearing in the recent literature, thus confirming the potential and efficiency of the proposed method.     

Upconversion-powered photoelectrochemistry

Upconversion photochemistry occurring between palladium(II) octaethylporphyrin (PdOEP, 1) and 9,10-diphenylanthracene (DPA, 2) in toluene successfully sensitizes nanostructured WO(3) photoanodes (E(g) = 2.7 eV) to sub-bandgap non-coherent green photons at low power density.     

Detection of multiple elements in coal samples from Bangladesh by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) was used to analyze the coal samples from the Barapukuria coal mine of Bangladesh and coal from eastern India. Besides the major elements carbon and silicon, a number of minor and trace elements, such as iron, titanium, aluminum, calcium, sodium, copper, zirconium, neodymium, ytterbium, cerium, samarium, dysprosium and gadolinium were identified. In earlier work some researchers identified the lines around 279 and 280 nm as due to Mg II rather than Yb III. The reasons for identifying these two lines as due to ytterbium in the present work are explained. The detection of multiple elements in one experiment in a commonly used fuel demonstrated the versatility and multi-elemental capability of LIBS.     

Sensing of 2,4,6‐Trinitrotoluene (TNT) and 2,4‐Dinitrotoluene (2,4‐DNT) in the Solid State with Photoluminescent RuII and IrIII Complexes

A series of metal–organic chromophores containing Ru^II or Ir^III were studied for the luminometric detection of nitroaromatic compounds, including trinitrotoluene (TNT). These complexes display long‐lived, intense photoluminescence in the visible region and are demonstrated to serve as luminescent sensors for nitroaromatics. The solution‐based behavior of these photoluminescent molecules has been studied in detail in order to identify the mechanism responsible for metal‐to‐ligand charge‐transfer (MLCT) excited state quenching upon addition of TNT and 2,4‐dinitrotoluene (2,4‐DNT). A combination of static and dynamic spectroscopic measurements unequivocally confirmed that the quenching was due to a photoinduced electron transfer (PET) process. Ultrafast transient absorption experiments confirmed the formation of the TNT radical anion product following excited state electron transfer from these metal complexes. Reported for the first time, photoluminescence quenching realized through ink‐jet printing and solid‐state titrations was used for the solid‐state detection of TNT; achieving a limit‐of‐quantitation (LOQ) as low as 5.6 ng cm^?2. The combined effect of a long‐lived excited state and an energetically favorable driving force for the PET process makes the Ru^II and Ir^III MLCT complexes discussed here particularly appealing for the detection of nitroaromatic volatiles and related high‐energy compounds.     

NHC-catalyzed annulation of enals and chalcones: further explorations on the novel synthesis of 1,3,4-trisubstituted cyclopentenes

The facile synthesis of 1,3,4-trisubstituted cyclopentenes via homoenolate annulation of enals with heterocycle substituted chalcones is described.     

N-Heterocyclic carbene (NHC) catalyzed annulation of enals and vinyl ketones: a novel synthesis of [2H]-pyranones

Homoenolate annulation of vinyl ketones led to the synthesis of dihydropyranones in contrast to cyclopentenes obtained by the homoenolate annulation of chalcones, another class of α,β-unsaturated ketones.     

Asymmetric Reduction of Alkyl-3-oxobutanoates by Candida parapsilosis ATCC 7330: Insights into Solvent and Substrate Optimisation of the Biocatalytic Reaction

Asymmetric reduction of alkyl-3-oxobutanoates mediated by Candida parapsilosis ATCC 7330 resulted in optically pure alkyl-3-hydroxybutanoates in good yields (up to 72 %) and excellent enantiomeric excess (up to >99 %). A detailed and systematic optimisation study was necessary and was carried out to avoid the undesired transesterification reaction during the course of asymmetric reduction. Under optimised conditions, the (S)-alkyl hydroxyesters were produced predominantly except for the methyl ester which formed the (R)-enantiomer. To the best of our knowledge, the biocatalytic asymmetric reduction of isoamyl-3-oxobutanoate to (S)-isoamyl-3-hydroxybutanoate is reported here for the first time.     

Application of a thermodynamically compatible two‐phase flow model to the high‐resolution simulations of compressible gas–magma flow

This paper reports on the application and development of a fully hyperbolic and fully conservative two‐phase flow model for the simulation of gas and magma flow within volcanic processes. The model solves a set of mixture conservation equations for the gas and magma two‐phase flow with velocity non‐equilibrium. In this model, the effect of the relative velocity is introduced by a kinetic constitutive equation with other equations for volume and mass fractions of the gas phase. The model is examined numerically by the widely used finite volume Godunov methods of centered‐type. Using the Riemann problem, we numerically simulate wave propagation and the development of shocks and rarefactions in volcanic eruptions. These simulations are of magma fragmentation type where the relative velocity continues to dominate. A series of test cases whose solution contains features relevant to gas–magma mixtures are conducted. In particular, numerical results indicate that the model implementation predicts key features of the relative velocity within volcanic processes without any mathematical or physical simplifications. Simulation results are sharply and accurately provided without any spurious oscillations in all of the flow variables. The numerical methods and results are also compared with other numerical methods available in the literature. It is found that the provided resolutions are more accurate for the considered test cases. Copyright © 2014 John Wiley & Sons, Ltd.     

Proteins: coexistence of stability and flexibility

We introduce an equation for protein native topology based on recent analysis of data from the Protein Data Bank and on a generalization of the Landau-Peierls instability criterion for fractals. The equation relates the protein fractal dimension df, the spectral dimension ds, and the number of amino acids N. Deviations from the equation may render a protein unfolded. The fractal nature of proteins is shown to bridge their seemingly conflicting properties of stability and flexibility. Over 500 proteins have been analyzed (df, ds, and N) and found to obey this equation of state.