Large eddy simulation of turbulent horizontal buoyant jets

Large eddy simulations (LESs) of turbulent horizontal buoyant jets are carried out using a high-order numerical method and Sigma subgrid-scale (SGS) eddy-viscosity model, for a number of different Reynolds (Re) and Richardson (Ri) numbers. Simulations at previous experimental flow conditions (Re = 3200, 24, 000 and Ri = 0, 0.01) are carried out first, and the results are found to be qualitatively and quantitatively similar to the experimental results, thus validating the numerical methodology. The effect of varying Ri (values 2×10^?4, 0.001, 0.005, and 0.01) and Re (3200 and 24, 000) is studied next. The presence of stable stratification on one side and unstable stratification on the other side of the jet centreline leads to an asymmetric development of horizontal buoyant jets. It is found that this asymmetry, the total radial spread and the vertical deflection are significantly affected by Ri, while Re affects only the radial asymmetry. The need for developing improved integral models, accounting for this asymmetry, is pointed out. Turbulent production and dissipation rates are investigated, and are found to be symmetric in the horizontal plane, but asymmetric in the mid-vertical plane. A previously proposed model, for correlation between the vertical component of the fluctuating scalar flux vector and the vertical cross-correlation component of the Reynolds tensor, is modified based on the current LES results. Instantaneous scalar and velocity fields are analysed to reveal the structure of horizontal buoyant jets. Similar to the developed turbulent jet, the flow close to the nozzle too is found to be markedly different in the stable and unstable stratification regions. Persistent coherent vortex rings are found in the stable stratification region, while intermittent breakdown of vortex rings into small-scale structures is observed in the unstable stratification region. Similarities and differences between the flow structures in the horizontal buoyant jet configuration and those in the jet in crossflow configuration are discussed. Finally, a dynamic mode decomposition analysis is carried out, which indicates that the flow in the unstable stratification region is more energetic and prone to instabilities, as compared to the flow in the stable stratification region.     

Simultaneous pursuit of out-of-sample performance and sparsity in index tracking portfolios

Index tracking is a passive investment strategy in which a fund (e.g., an ETF: exchange traded fund) manager purchases a set of assets to mimic a market index. The tracking error, i.e., the difference between the performances of the index and the portfolio, may be minimized by buying all the assets contained in the index. However, this strategy results in a considerable transaction cost and, accordingly, decreases the return of the constructed portfolio. On the other hand, a portfolio with a small cardinality may result in poor out-of-sample performance. Of interest is, thus, constructing a portfolio with good out-of-sample performance, while keeping the number of assets invested in small (i.e., sparse). In this paper, we develop a tracking portfolio model that addresses the above conflicting requirements by using a combination of L0- and L2-norms. The L2-norm regularizes the overdetermined system to impose smoothness (and hence has better out-of-sample performance), and it shrinks the solution to an equally-weighted dense portfolio. On the other hand, the L0-norm imposes a cardinality constraint that achieves sparsity (and hence a lower transaction cost). We propose a heuristic method for estimating portfolio weights, which combines a greedy search with an analytical formula embedded in it. We demonstrate that the resulting sparse portfolio has good tracking and generalization performance on historic data of weekly and monthly returns on the Nikkei 225 index and its constituent companies.     

Application of medium energy plasma focus device in study of radioisotopes

Pulsed neutrons generated in a plasma focus device are used for the thermal neutron activation analysis (TNAA) of selected three elements having widely different half-lives varying from a few seconds to a few days [Dysprosium (Dy), Manganese (Mn) and Gold (Au)]. Neutron pulse having strength of $(1.2\pm 0.3)\times {10}^9$ neutrons/pulse with a pulse width of $46\pm 5\text{ns}$ is produced by “MEPF-12” device operated at a filling gas (deuterium + 0.5% krypton) pressure of 3 mbar. The fast 2.45 MeV D–D neutrons are thermalized before irradiating the sample. The decay gammas from the radioisotopes ^165mDy ($T_{1/2}=1.26\text{min.}$), ⁵⁶Mn ($T_{1/2}=2.58\text{hrs.}$), and ¹⁹⁸Au ($T_{1/2}=2.69\text{days}$) produced via reactions, ¹⁶⁴Dy($n,\gamma$)^165mDy, ⁵⁵Mn($n,\gamma$) ⁵⁶Mn, and ¹⁹⁷Au($n,\gamma$) ¹⁹⁸Au respectively are counted off-line in a lead shielded well type $76\times 76{\text{mm}}^2$ NaI(Tl) detector coupled to a calibrated 2048 channel analyzer. The values of half-lives evaluated from the measured decay gammas, $1.43\pm 0.3\text{min.}$, $2.56\pm 0.5\text{hrs.}$ and $2.84\pm 0.6\text{days}$ respectively for the radioisotopes of Dy, Mn and Au, are seen to be close to the values reported in literature.     

Synthesis of the necine bases (±)-macronecine and (±)-supinidine via an aza-ene reaction and allylsilane induced ring closure

An aza-ene reaction has been used for the first time for the synthesis of two 5-membered lactam-hydrazides, each with a built-in allylsilane terminator for further elaboration. One of the lactam-hydrazides was transformed via an allylsilane-hydrazonium ion ring closure to a fused tetrahydropyrazole which may be considered as a mono-nitrogen analog of the biologically significant necine bases. A density functional theoretical study (B3LYP/6-21G*) was undertaken to provide insight into the factors that favor a synclinal transition structure of the hydrazonium ion intermediate leading to the tetrahydropyrazole. This stereocontrolled synthesis served as a model for the multi-step conversion of the other lactam-hydrazide, the substituted 2-pyrrolidinone, to necine bases (±)-supinidine and (±)-macronecine. An allylsilane-aldehyde ring closure formed the key step in the synthesis of these natural products.     

Fingerprint analysis of Shankhpushpi for species discrimination by HPLC coupled with chemometric methods

Abstract

Shankhpushpi, traded in the Indian market is having different controversial botanical sources, that is, Convolvulus pluricaulis Choisy (Convulvulaceae), Clitoria ternatea Linn. (Papilionaceae), and Evolvulus alsinoides Linn. (Convulvulaceae). Simple, accurate and precise RP-HPLC-PDA method was established for quality assessment and discrimination of Shankhpushpi samples using chromatographic profiling method. In distinction to the routine method of quality assessment which uses single or dual marker peaks, all chromatographic data (retention times/variables) were used. Fifteen shankhpushpi samples were purchased from the market including authenticated samples of all three C. pluricaulis, C. ternatea, E. alsinoides. A total of 18 samples were analyzed by HPLC and the dataset was then treated with multivariate analyses like PCA and HCA by using MINITAB software. Thus, the developed method was useful in discriminating the Shankhpushpi samples and for the perseverance of quality control.     

Catalytic activities of Schiff base aquocomplexes of copper(II) towards hydrolysis of amino acid esters

Summary Solid aquo Cu^II complexes of Schiff bases derived from amino acids have been prepared and characterized. Using a pH-stat method, the kinetics of base hydrolysis of the amino acid esters H₂NCH₂CO₂Me·HCl (GE), (HO)-C₆H₄CH₂(NH₂)CO₂Me·HCl (TE), MeS(CH₂)₂CH(NH₂)-CO₂Me·HCl (ME), HSCH₂CH(NH₂)CO₂Et·HCl (CE), C₃H₃N₂CH₂CH(NH₂)CO₂Me·2HCl (HE) and [—SCH₂-CH(NH₂)CO₂Me]₂·2HCl (CysE) have been studied. The complexes enhanced the rate of hydrolysis substantially, the values of the second-order rate constants being some 10–50 times greater than those obtained in the presence of the simple Cu^II ion.     

Revealing the bonding of solvated Ru complexes with valence-to-core resonant inelastic X-ray scattering

Ru-complexes are widely studied because of their use in biological applications and photoconversion technologies. We reveal novel insights into the chemical bonding of a series of Ru(ii)- and Ru(iii)-complexes by leveraging recent advances in high-energy-resolution tender X-ray spectroscopy and theoretical calculations. We perform Ru 2p4d resonant inelastic X-ray scattering (RIXS) to probe the valence excitations in dilute solvated Ru-complexes. Combining these experiments with a newly developed theoretical approach based on time-dependent density functional theory, we assign the spectral features and quantify the metal–ligand bonding interactions. The valence-to-core RIXS features uniquely identify the metal-centered and charge transfer states and allow extracting the ligand-field splitting for all the complexes. The combined experimental and theoretical approach described here is shown to reliably characterize the ground and excited valence states of Ru complexes, and serve as a basis for future investigations of ruthenium, or other 4d metals active sites, in biological and chemical applications.

Combined experimental and theoretical Ru 2p4d resonant inelastic X-ray scattering study probes the chemical bonding and the valence excited states of solvated Ru complexes.