Excitation spectra of dibenzoborole containing pi-electron systems: controlling the electronic spectra by changing the p(pi)-pi* conjugation

We report time-dependent density functional theory calculations of the vertical excitation energies for the singlet states of three-coordinate 5H-dibenzoborole (DBB) derivatives and four-coordinate 5-fluoro-5H-dibenzoborole ion (FDBB) derivatives. These molecules show remarkable hypsochromic (blue) shifts in their fluorescence spectra and bathochromic (red) shifts in their absorption spectra when the bridging boron atoms change their coordination number from three to four. We constructed a series of derivatives of DBB and FDBB and studied how the energies of the electronic excitations change. The states with prominent oscillator strength in all of the DBB and FDBB derivatives show similar shifts of their excitation energies upon coordination. The three-coordinate DBB derivative 5-(2,4,6-triisopropylphenyl)-2,8-dimethoxy-3,7-bis[p-(N,N-diphenylamino)phenyl]-5H-dibenzo[d,b]borole has an intense absorption at 3.25 eV, which shifts in the four-coordinate FDBB derivative 5-fluro-5-(2,4,6-triisopropylphenyl)-2,8-dimethoxy-3,7-bis[p-(N,N-dip henylamino)phenyl]-5H-dibenzo[d,b]borole ion to 3.17 eV. The experimental absorption peaks are 3.43 and 3.31 eV, respectively. In addition, we investigated and analyzed the nature of these electronic excitations using attachment/detachment density plots, with which we characterized the changes in electron density that arose from the excitations.     

Recent developments in the metal catalysed cross-coupling reactions for the synthesis of the enone system of chalcones

For the last two decades, chalcones and their derivatives have attracted special interest among researchers due to their pharmaceutical properties. Numerous research works have been still going on to improve the methodologies of chalcone synthesis. Chalcone has displayed a remarkable curative efficiency to cure numerous diseases and it continues to show promise for new drug investigations. This review highlights the metal catalysed cross-coupling reactions for the synthesis of chalcone and its derivatives from 2009 to 2020.     

Growth and characterization of metal ions doped l-serine NLO single crystals for optoelectronic applications

Single crystals of pure and metal ions (K⁺, Na⁺ and Li⁺) doped l-serine have been grown by slow evaporation solution growth technique (SEST). Energy dispersive X-ray analysis (EDAX) and inductively coupled plasma optical emission spectroscopy (ICP-OES) prove the incorporation of metal ions into the doped crystals. The lattice parameters have been obtained from single crystal X-ray diffraction (XRD) studies. The presence of functional groups is identified by Fourier transform infrared (FTIR) and FT-RAMAN analyses. The thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) reveal that the thermal stability of lithium doped l-serine crystal is enhanced. The mechanical properties have been studied by vicker's microhardness test. UV–vis-NIR spectroscopy shows that the percentage of transmission is increased in lithium doped l-serine crystals. Potassium and lithium ions doped l-serine crystals have enhanced second harmonic generation (SHG) efficiency indicating that these crystals are potential candidates for non linear optical (NLO) applications.     

Regulation of heat transfer in Rayleigh–Bénard convection in Newtonian liquids and Newtonian nanoliquids using gravity,boundary temperature and rotational modulations

Journal of Thermal Analysis and Calorimetry - The individual effect of time-periodic gravity modulation, in-phase and out-of-phase temperature modulations and rotational modulation on...     

Chemometrics-assisted cross injection analysis for simultaneous determination of phosphate and silicate

This work presents a novel method for simultaneous spectrophotometric determination of phosphate and silicate by using a cross injection analysis (CIA) coupled with the use of partial least squares (PLS) for data evaluation. The detection principle is based on the well-known ‘molybdenum blue’ method. The molybdate ions in the presence of stannous chloride in acidic medium give phosphomolybdenum blue and silicomolybdenum blue as products. In this work, all the liquids, including sample and reagents were simultaneously introduced into a CIA platform by using two peristaltic pumps for controlling the x-channel and y-channel flow which was automatically manipulated by using in-house control board. Crossflow provides sufficient mixing inside the platform prior detection of the absorption spectra of blue complexes in the wavelength of 400–900 nm. Since spectra of the blue colour product of phosphate and silicate are resemblant, these two analytes therefore reciprocally interfere with one another. This results in difficulty in simultaneous analysis of phosphate and silicate. In this work, PLS was utilised as assistor of CIA system for simultaneous analysis of phosphate and silicate using molybdenum blue reaction without using any modification of reagents and addition of selective masking agent. The calibration ranges are 0.1–6 mgP L^?1 and 5–100 mgSi L^?1 for phosphate and silicate, respectively. By using CIA coupled with PLS for data evaluation, the analysis of two analytes was achieved within 1.5 min with only single injection. The developed system was applied to natural water samples and the system was validated with the conventional methods. By statistical paired t-test, there was no evidence of significant difference at 95% confidence level (t_stat = 2.28, t_critical = 2.31 and t_stat = 0.62, t_critical = 2.31 for phosphate and silicate, respectively). This implied that the chemometrics-assisted CIA system was successfully developed for simultaneous spectrophotometric determination of phosphate and silicate.     

Lattice instability and martensitic transformation in LaAg predicted from first-principles theory

The electronic structure, elastic constants and lattice dynamics of the B(2) type intermetallic compound LaAg are studied by means of density functional theory calculations with the generalized gradient approximation for exchange and correlation. The calculated equilibrium properties and elastic constants agree well with available experimental data. From the ratio between the bulk and shear moduli, LaAg is found to be ductile, which is unusual for B(2) type intermetallics. The computed band structure shows a dominant contribution from La 5d states near the Fermi level. The phonon dispersion relations, calculated using density functional perturbation theory, are in good agreement with available inelastic neutron scattering data. Under pressure, the phonon dispersions develop imaginary frequencies, starting at around 2.3 GPa, in good accordance with the martensitic instability observed above 3.4 GPa. By structural optimization the high pressure phase is identified as orthorhombic B(19).     

Superparamagnetic nanoparticle-polystyrene bead conjugates as pathogen capture mimics: a parametric study of factors affecting capture efficiency and specificity

There is currently significant interest in the miniaturization of disease detection platforms. As detection platforms decrease in size there is a need for the development of sample preparation protocols by which cells or biomarkers of interest can be concentrated from large volumes down to volumes more amenable to analysis within microfluidic devices. To address this issue, we present a series of magnetic confinement assays for polystyrene (PS) beads mediated through their covalent modification with a series of superparamagnetic nanoparticles, where the PS beads have many properties similar to bacteria, but are not pathogenic. The magnetic confinement of the PS beads is investigated as a function of (1) the overall nanoparticle size, (2) the loading of superparamagnetic content within the nanoparticle matrix, and (3) the viscosity and volume of the dispersion medium. We demonstrate that the time required for the magnetic capture of the PS beads by the superparamagnetic nanoparticles (1) decreases as the loading of superparamagnetic material into the nanoparticles increases and (2) increases as the viscosity and volume of the dispersion medium are increased. However, limitations in the magnetic confinement efficiency for the PS beads labeled with nanoparticles comprised of low loadings of superparamagnetic material can be overcome through the use of magnetic columns. These magnetic columns provide a practical and fast mode of sample preparation that should facilitate the magnetic concentration of cells and biomarkers from large volumes to volumes more amenable to incorporation into a microfluidic-based analysis system, where they can be analyzed/detected.     

Kinetic-spectrophotometric method for the determination of trace amounts of bromide in seawater

A novel simple, sensitive and rapid kinetic-spectrophotometric method is proposed for the determination of trace amounts of bromide. The method is based on its catalytic effect on the oxidation of methylene blue (MB) by hydrogen peroxide in strongly acidic solution. The oxidation reaction is activated by large amounts of chloride and can be monitored spectrophotometrically by measuring the decrease in the absorbance of MB at 746 nm. The determination of bromide is performed by a fixed-time method at the first 100 s from the initiation of the reaction. Unlike other kinetic-spectrophotometric methods for the determination of bromide, the proposed method does not require heating the solution. Bromide can be determined in the range from 80 to 960 μg l⁻¹ with the detection limit of 35 μg l⁻¹. The relative standard deviation of ten replicate determination of 480 μg l⁻¹ bromide was 1.4%. The influence of potential interfering ions was studied. The proposed method was satisfactorily applied to the determination of bromide in seawater without interfering effect from chloride ion.     

Effect of trigonometric sine,square and triangular wave-type time-periodic gravity-aligned oscillations on Rayleigh–Bénard convection in Newtonian liquids and Newtonian nanoliquids

The influence of trigonometric sine, square and triangular wave-types of time-periodic gravity-aligned oscillations on Rayleigh–Bénard convection in Newtonian liquids and in Newtonian nanoliquids is studied in the paper using the generalized Buongiorno two-phase model. The five-mode Lorenz model is derived under the assumptions of Boussinesq approximation, small-scale convective motion and some slip mechanisms. Using the method of multiscales, the Lorenz model is transformed to a Ginzburg–Landau equation the solution of which helps in quantifying the heat transport through the Nusselt number. Enhancement of heat transport in Newtonian liquids due to the presence of nanoparticles/nanotubes is clearly explained. The study reveals that all the three wave types of gravity modulation delay the onset of convection and thereby to a diminishment of heat transport. It is also found that in the case of trigonometric sine type of gravity modulation heat transport is intermediate to that of the cases of triangular and square types. The paper is the first such work that attempts to theoretically explain the effect of three different wave-types of gravity modulation on onset of convection and heat transport in the presence/absence of nanoparticles/nanotubes. Comparing the heat transport by the single-phase and by the generalized two-phase models, the conclusion is that the single-phase model under-predicts heat transport in nanoliquids irrespective of the type of gravity modulation being effected on the system. The results of the present study reiterate the findings of related experimental and numerical studies.

     

A new azafluorenone from the roots of Polyalthia cerasoides and its biological activity

Chromatographic separation of the ethyl acetate extract of roots of Polyalthia cerasoides has led to the isolation of the new compound, 6,8-dihydroxy-7-methoxy-1-methyl-azafluorenone. This compound exhibited potent cytotoxic activities with IC50 values in the range of 2.64-3.58 microg x mL(-1) for A549, GLC4 and GLC4/Adr cells, but was not recognized by ABCC1/MRP1 protein. The compound also showed very strong inhibition of M. tuberculosis using a broth microdilution method, with an MIC value of 0.78 microg x mL(-1), which was equal to that of ofloxacin, one of the four antibiotic drugs used as a positive control.