Investigations on the geometrical isomers of astaxanthin: Raman spectroscopy of conjugated polyene chain with electronic and mechanical confinement

Recent research interests in geometrical isomers of astaxanthin (AST) are motivated by their metabolic activities in aquatic animals and human. It has been established that cis‐isomers of AST are selectively absorbed in human plasma during the metabolic process; however, exact absorption mechanism is still unclear. Hence, a detailed investigation of the structural and optical properties of geometrical isomers of AST is required. Among the techniques available for the study of AST and other carotenoids, Raman spectroscopy has been much acclaimed. Raman spectra have been shown to be influenced by the electronic and mechanical confinement effects arising from the conjugated polyene chain of carotenoids. In this work, we present Raman studies of geometrical isomers of AST, along with their optical absorption characteristics. Geometrical isomers of AST were prepared by heating all trans‐AST in solution form, and the isomers were separated using high performance liquid chromatography. Optical absorption spectra of cis‐isomers of AST showed hypsochromic shifts in the main absorption band and formation of new bands at lower wavelengths. A detailed Raman spectral analysis performed on the cis‐isomers of AST showed new modes which have not been observed and accounted for so far. In addition, we demonstrate that the electronic and mechanical confinement effects in the polyene chain of AST play an important role in the Raman spectra of geometrical isomers of AST. It is anticipated that this work will demonstrate that Raman spectroscopy is an important diagnostic tool in distinguishing and identifying the geometrical isomers of AST. Copyright © 2014 John Wiley & Sons, Ltd.     

A study on the influence of dysprosium cation substitution on the structural, morphological, and electrochemical properties of lithium manganese oxide

The synthesis of series of dysprosium-doped lithium manganese oxide in the general formula LiDy _x Mn_2?x O4 (x?=?0.0, 0.05, 0.1, 0.15, and 0.2) using double stage coprecipitation method followed by microwave heat treatment is reported. The characterization results of X-ray diffraction and infrared spectroscopy have illustrated the cubic structure for all the compounds. The lattice parameter has been observed to decrease with dysprosium doping. The influence of doping in elastic property of the samples has been studied with infrared spectroscopy. The grain size of the LiDy_0.05Mn_1.95O₄ has been observed to be less than 1???m. The Image J software has been used to further analyze the micrographs. The initial capacity of the samples are observed to decrease with Dy³⁺ doping, but the capacity retention after 50 cycles for Dy 0.05, 0.1, 0.15, and 0.2 samples are reported as 95.4%, 93.2%, 91.3%, and 87.7%, respectively. The electrochemical impedance spectra has been performed to analyze the effectiveness of Dy³⁺ ion doping and the act of Dy doping has been observed to reduce the charge transfer resistance and increase the Li ion diffusion coefficient.     

Model-based likelihood ratio confidence intervals for survival functions

We introduce an adjusted likelihood ratio procedure for computing pointwise confidence intervals for survival functions from censored data. The test statistic, scaled by a ratio of two variance quantities, is shown to converge to a chi-squared distribution with one degree of freedom. The confidence intervals are seen to be a neighborhood of a semiparametric survival function estimator and are shown to have correct empirical coverage. Numerical studies also indicate that the proposed intervals have smaller estimated mean lengths in comparison to the ones that are produced as a neighborhood of the Kaplan-Meier estimator. We illustrate our method using a lung cancer data set.     

Acoustic classification of multiple simultaneous bird species: a multi-instance multi-label approach

Although field-collected recordings typically contain multiple simultaneously vocalizing birds of different species, acoustic species classification in this setting has received little study so far. This work formulates the problem of classifying the set of species present in an audio recording using the multi-instance multi-label (MIML) framework for machine learning, and proposes a MIML bag generator for audio, i.e., an algorithm which transforms an input audio signal into a bag-of-instances representation suitable for use with MIML classifiers. The proposed representation uses a 2D time-frequency segmentation of the audio signal, which can separate bird sounds that overlap in time. Experiments using audio data containing 13 species collected with unattended omnidirectional microphones in the H. J. Andrews Experimental Forest demonstrate that the proposed methods achieve high accuracy (96.1% true positives/negatives). Automated detection of bird species occurrence using MIML has many potential applications, particularly in long-term monitoring of remote sites, species distribution modeling, and conservation planning.     

Unsteady fluid flow and heat transfer over a bank of flat tubes

Transient numerical simulations of fluid flow and heat transfer over a bank of flat tubes have been carried for both in-line and staggered configurations for the following boundary conditions: (a) isothermal and (b) isoflux. The effect of Reynolds number, Prandtl number, length ratio, and the height ratio, on the Nusselt number, and the dimensionless pressure drop are elucidated. Correlations are proposed for both pressure drop and Nusselt number and optimum configurations have been determined.     

Interaction of turbulent natural convection and surface thermal radiation in inclined square enclosures

Two-dimensional numerical studies of flow and temperature fields for turbulent natural convection and surface radiation in inclined differentially heated enclosures are performed. Investigations are carried out over a wide range of Rayleigh numbers from 10⁸ to 10¹², with the angle of inclination varying between 0° and 90°. Turbulence is modeled with a novel variant of the k–ε closure model. The predicted results are validated against experimental and numerical results reported in literature. The effect of the inclination of the enclosure on pure turbulent natural convection and the latter’s interaction with surface radiation are brought out. Profiles of turbulent kinetic energy and effective viscosity are studied to observe the net effect on the intensity of turbulence caused by the interaction of natural convection and surface radiation. The variations of local Nusselt number and average Nusselt number are presented for various inclination angles. Marked change in the convective Nusselt number is found with the orientation of enclosure. Also analyzed is the influence of change in emissivity on the flow and heat transfer. A correlation relevant to practical applications in the form of average Nusselt number, as a function of Rayleigh number, Ra, radiation convection parameter, N _RC and inclination angle of the enclosure, φ is proposed.     

Gibbs Transfer Energies of Macrocyclic Ligands in Methanol+N-methyl-2-pyrrolidinone Mixtures by Solubility and Partition Measurements

The standard Gibbs transfer energies of 18-crown-6,dibenzo-18-crown-6, cryptands 21, 22 and 222 frommethanol to methanol + N-methyl-2-pyrrolidinone(NMP) mixtures were determined from solubility andpartition measurements at 30 °C. While the Gibbs energy of transfer of 18-C-6 is positive,increases up to X_NMP = 0.7 and thereafter decreases, the transfer energy ofdibenzo-18-C-6 is negative and decreases with the addition of NMP. However,the transfer energy of cryptand 21becomes increasingly negative with theaddition of NMP while that of cryptand 22 ispositive and increases under the sameconditions. For cryptand 222, the transferenergy is slightly negative up toX_NMP = 0.5 butdecreases markedly at higher compositions of NMP. These results have been explainedin terms of the various types of interaction between the ligand molecules, solventcomponents and the effect of solvent–solvent interactions on them.     

Effect of Polydispersity on the Phase Behavior of Polymer Blends

Summary: The effect of polydispersity on polymer blend phase behavior is studied by in situ small‐angle X‐ray scattering. In a polydisperse polyethylene (PE)/isotactic poly(propylene) (iPP) blend, the enthalpic portion of the interaction parameter is greater than that of a corresponding blend with lower polydispersity. This is attributed to the presence of long chains, which provide a higher interaction energy and packing constraint, reducing the system miscibility. As expected, the radius of gyration is higher in the system with higher polydispersity.

Comparison of phase diagrams of the iPP/PE system used in this study (thin lines) with that obtained from the literature (thick lines). The solid lines represent binodals and the dashed lines are spinodals.     

Bismuth-Oxide-Decorated Graphene Oxide Hybrids for Catalytic and Electrocatalytic Reduction of CO2

Global warming challenges are fueling the demand to develop an efficient catalytic system for the reduction of CO₂, which would contribute significantly to the control of climate change. Herein, as-synthesized bismuthoxide-decorated graphene oxide (Bi₂O₃@GO) was used as an electro/thermal catalyst for CO₂ reduction. Bi₂O₃@GO is found to be distributed uniformly, as confirmed by scanning electron and transmission electron microscopic analysis. The X-ray diffraction (XRD) pattern shows that the Bi₂O₃ has a β-phase with 23.4 m² g⁻¹ BET surface area. Significantly, the D and G bands from Raman spectroscopic analysis and their intensity ratio (I_D/I_G) reveal the increment in defective sites on GO after surface decoration. X-ray photoelectron spectroscopic (XPS) analysis shows clear signals for Bi, C, and O, along with their oxidation states. An ultra-low onset potential (−0.534 V vs. RHE) for the reduction of CO₂ on Bi₂O₃@GO is achieved. Furthermore, potential-dependent (−0.534, −0.734, and −0.934 vs. RHE) bulk electrolysis of CO₂ to formate provides Faradaic efficiencies (FE) of approximately 39.72, 61.48, and 83.00 %, respectively. Additionally, in time-dependent electrolysis at a potential of −0.934 versus RHE for 3 and 5 h, the observed FEs are around 84.20 % and 87.17 % respectively. This catalyst is also used for the thermal reduction of CO₂ to formate. It is shown that the thermal reduction provides a path for industrial applications, as this catalyst converts a large amount of CO₂ to formate (10 mm ).     

Direct Catalytic Asymmetric Addition of α-Fluoronitriles to Aldehydes

A fluorine-containing tetrasubstituted stereogenic center is a highly valued structural feature in medicinal chemistry. Herein, we describe the direct coupling of racemic α-fluoronitriles and aldehydes promoted by a chiral Cu^I/Barton's base catalytic system, delivering α-tetrasubstituted α-fluoro-β-hydroxynitriles with satisfactory stereoselection. The stereochemical course was positively biased by the combined use of asymmetrical achiral thiourea as a supplementary ligand for Cu^I, which significantly enhanced the stereoselectivity. Both aromatic and aliphatic aldehydes were implemented to provide densely and stereoselectively functionalized chiral building blocks with aliphatic and aromatic tails.