A stochastic model for solidification II. Application to binary metallic melts

A stochastic model to study the solidifcation process developed in part I is applied to various binary alloys having different values of interaction energies. The results obtained for the time evolution of temperature and concentration, rate of growth and shape of the solid-liquid interface are presented.     

Ionic conductivity, structural and thermal properties of pure and Sr doped Y2Ti2O7 pyrochlores for SOFC

In the present study, SrO doped Yttrium titanate pyrochlore was synthesized using solid state reaction technique. The sintering characteristics, crystal structure, thermal and conductivity behavior of doped and undoped pyrochlores have been studied to find their suitability in solid oxide fuel cells (SOFC). The as-prepared samples were characterized using X-ray diffraction (XRD), Fourier-Transform-Infrared spectroscopy (FT-IR), thermal-gravimetric analysis (TGA) and ac conductivity up to 900 °C. The results are discussed in light of oxygen vacancy formation and structural disordering. Undoped and doped yttrium titanate with SrO (x = 0.1) exhibits single Y₂Ti₂O₇ phase with relative density of 94%. It was observed that further doping of SrO (x = 0.2–0.4) leads to formation of Y₂Ti₂O₇ phase along with SrTiO₃ phase. Excessive SrO (x = 0.4) results in increase in ionic conductivity to 1.50 × 10⁻¹ S cm⁻¹ whereas it impedes the densification process with relative density of 85%.     

One-pot efficient synthesis of dimeric, trimeric, and tetrameric BODIPY dyes for panchromatic absorption

One-pot Knoevenagel self-condensation reaction of β-formyl BODIPY dye bearing a formyl group at 2-position offered dimeric, trimeric and tetrameric BODIPY dyes containing a formyl capping end group, exhibiting panchromatic absorption.     

Theoretical investigation of zero field splitting parameters for Mn2+ centres in L-asparagine monohydrate

Zero-field splitting (ZFS) parameters D and E are calculated using the point-charge model (PCM) and superposition model (SPM) for Mn(2+) centre in L-asparagine monohydrate (LAM) single crystal. The calculated ZFS parameters obtained using these two models are compared with the experimental values for interstitial site of Mn(2+). The SPM and PCM give ZFS parameters similar to those of experimental ones. This supports the notion that the impurity ion occupies interstitial site in LAM.     

Supramolecular assembly of a biomineralizing antimicrobial peptide in coarse-grained Monte Carlo simulations

Monte Carlo simulations are used to model the self-organizing behavior of the biomineralizing peptide KSL (KKVVFKVKFK) in the presence of phosphate. Originally identified as an antimicrobial peptide, KSL also directs the formation of biosilica through a hypothetical supramolecular template that requires phosphate for assembly. Specificity of each residue and the interactions between the peptide and phosphate are considered in a coarse-grained model. Both local and global physical quantities are calculated as the constituents execute their stochastic motion in the presence and absence of phosphate. Ordered peptide aggregates develop after simulations reach thermodynamic equilibrium, wherein phosphates form bridging ligands with lysines and are found interdigitated between peptide molecules. Results demonstrate that interactions between the lysines and phosphate drive self-organization into lower energy conformations of interconnected peptide scaffolds that resemble the supramolecular structures of polypeptide- and polyamine-mediated silica condensation systems. Furthermore, the specific phosphate-peptide organization appears to mimic the zwitterionic structure of native silaffins (scaffold proteins of diatom shells), suggesting a similar template organization for silica deposition between the in vitro KSL and silaffin systems.     

Scaffolding of an antimicrobial peptide (KSL) by a scale-down coarse-grained approach

A coarse-grained approach with enhanced representation of amino acid (involving four components, i.e. a central alpha carbon and its side group along with C and N terminals) is used to study the multi-scale assembly of an antimicrobial peptide (KSL) in an explicit solvent (in a scale-down hierarchy of Eby et al. [Phys. Chem. Chem. Phys., 2011, 13, 1123-1130]). Both local (mobility, solvent-surrounding, energy profiles) and global (variation of the root mean square displacement of peptides and its gyration radius with time steps, radial distribution function, and structure factors) physical quantities are analyzed as a function of the solvent quality (i.e. the solvent-residue interaction strength). We find that the mobility of the interacting side group (lysine) decays as the number of its surrounding solvent constituents grows systematically on increasing the interaction strength. Pinning of lysine directs the underlying segmental conformation that propagates to larger scale scaffolding. The radial distribution function (a measure of the correlated peptide assembly) decays with the distance (faster with stronger solvent interaction). Scaling of the structure factor (S(q)) of peptide assembly with the wave vector q = 2π/λ (λ is the wavelength), S(q) ∝q(-1/ν) provides an insight into its multi-scale mass (N) distribution. The effective dimension D(e) = 1/ν of the peptide assembly over the spatial distribution (R) can be estimated using N∝R(D(e)). On scales larger than the size (i.e. the radius of gyration R(g)) of the peptide, D(e) ≈ 1.303 ± 0.070 to D(e) ≈ 1.430 ± 0.096, a rather fibrous morphology appears perhaps due to directed pinning while the morphology appears like an ideal chain, D(e) ≈ 1.809 ± 0.017 to D(e) ≈ 1.978 ± 0.017, at a smaller scale R≤R(g).     

Immobilization of chiral oxazaborolidine catalyst over highly ordered 3D mesoporous silica with Ia3d symmetry for enantioselective reduction of prochiral ketone

Here we demonstrate for the first time the encapsulation of a chiral oxazaborolidine complex in the 3D mesoporous channels of an amine functionalized KIT-6 material via covalent bonding through a post-synthetic approach. The physico-chemical properties of the pure and immobilized KIT-6 catalysts were obtained by various techniques such as XRD, nitrogen adsorption, HRSEM, UV-Vis diffuse reflectance spectroscopy, and FT-IR spectroscopy. It has been found that the structural stability of the KIT-6 was not affected even after the immobilization of a significant amount of chiral ligand inside the mesoporous channels of the support. However, the values of structural parameters such as the specific surface area and the specific pore volume of the KIT-6 support was significantly lower than the pure KIT-6 support. The chemical interaction between the chiral ligand inside the mesochannels and the KIT-6 support was also confirmed by UV-Vis and FT-IR spectroscopy. The chiral catalytic performance of the immobilized catalysts for the enantioselective reduction of aromatic prochiral ketones was demonstrated and the results were compared with chiral catalyst immobilized supports with uni-dimensional porous structures, such as MCM-41 and SBA-15. Among the catalysts studied, chiral catalyst immobilized KIT-6 showed the highest performance with a high product yield and a high enantioselectivity due to its 3D porous structure with two continuous and interpenetrating systems of chiral channels and an interwoven 3D cylindrical type pores of Ia3d symmetry. The catalyst also exhibited much better recycling capability than other chiral catalyst supported mesoporous materials used in the study.     

Terpenoid composition and antifungal activity of three commercially important essential oils against Aspergillus flavus and Aspergillus niger

Hydro-distilled essential oils extracted from three commercially important aromatic plants were analysed by capillary gas chromatography-flame ionization detector and gas chromatography/quadrupole mass spectrometry and subjected to antifungal activity. Fifteen compounds, which accounted for 97.8% of Acorus calamus root oil composition have been identified. Besides the major constituent (Z)-asarone (81.1-92.4%), (Z)-methyl isoeugenol (1.8-2.1%), (Z)-isoelemicin (1.2-1.3%), (E)-asarone (1.0-2.6%), (E)-methyl isoeugenol (0.2-0.4%), (Z)-β-ocimene (0.2-0.4%), elemicin (0.2-0.3%), linalool (0.1-0.9%) and kessane (t-0.2%) were identified. Monoterpenes constituted the main fraction of Origanum vulgare essential oil attaining 90.5% of the total oil composition. p-Cymene (10.3%) was the major component of the monoterpene hydrocarbon fraction while thymol (53.2%) and carvacrol (3.9%) were the most abundant oxygenated monoterpenes among the 33 identified constituents. Cinnamomum tamala leaf oil contained (E)-cinnamaldehyde as the principal component. Quantitative variations in (Z)-cinnamaldehyde (5.8-7.1%), linalool (6.4-8.5%) and (E)-cinnamyl acetate (4.7-5.2%) were significant. The antifungal activity of the hydro-distilled essential oils of A. calamus, O. vulgare and C. tamala were evaluated against Aspergillus flavus and Aspergillus niger. Disc diffusion method was used for the determination of the inhibitory effect. O. vulgare essential oil exhibited the highest activity. Moreover, all three essential oils inhibit the growth of A. flavus and A. niger.