Determination of selenomethionine by high performance liquid chromatography-direct hydride generation-atomic absorption spectrometry

A simple, reliable, trace determination of selenomethionine (Semet) based on a direct hydride generation atomic absorption spectrometric method was developed using sodium tetrahydroborate (0.3% in 0.2% NaOH) and hydrochloric acid (3 M). The method excluded any chemical pretreatment prior to hydride generation (HG). The optimized HG system was successfully coupled with the HPLC system. The detection limit (3σ of blank; n=5), reproducibility (R.S.D. of three successive analyses/day, performed on three different days), and repeatability (R.S.D. of three successive analyses) of the method were 1.08 ng ml⁻¹, 9.8% for 9.04 ng ml⁻¹ and 2.1–9.5% for 30.0–1.27 ng ml⁻¹ Semet as Se (standards prepared in Milli-Q water). Calibration graph was linear up to 30 ng ml⁻¹. This HPLC-HG-AAS method is very promising and successfully determined Semet (spiked) in human urine.     

A hybrid FVM–LBM method for single and multi‐fluid compressible flow problems

The lattice Boltzmann method (LBM) has established itself as an alternative approach to solve the fluid flow equations. In this work we combine LBM with the conventional finite volume method (FVM), and propose a non‐iterative hybrid method for the simulation of compressible flows. LBM is used to calculate the inter‐cell face fluxes and FVM is used to calculate the node parameters. The hybrid method is benchmarked for several one‐dimensional and two‐dimensional test cases. The results obtained by the hybrid method show a steeper and more accurate shock profile as compared with the results obtained by the widely used Godunov scheme or by a representative flux vector splitting scheme. Additional features of the proposed scheme are that it can be implemented on a non‐uniform grid, study of multi‐fluid problems is possible, and it is easily extendable to multi‐dimensions. These features have been demonstrated in this work. The proposed method is therefore robust and can possibly be applied to a variety of compressible flow situations. Copyright © 2009 John Wiley & Sons, Ltd.     

An eco-safe approach to benzopyranopyrimidines and 4H-chromenes in ionic liquid at room temperature

An environmentally benign, ionic liquid promoted multicomponent protocol to benzopyrano(2,3-d)pyrimidines and 4H-chromenes has been developed at room temperature. Results of the reaction depend on the nature of the nucleophile used in the reaction. Secondary amines result in the formation of benzopyrano(2,3-d)pyrimidines, whereas thiols give rise to 4H-chromenes under the same set of reaction conditions.     

Surrogate-based modeling and dimension reduction techniques for multi-scale mechanics problems

Successful modeling and/or design of engineering systems often requires one to address the impact of multiple "design variables" on the prescribed outcome.There are often multiple,competing objectives based on which we assess the outcome of optimization.Since accurate,high fidelity models are typically time consuming and computationally expensive,comprehensive evaluations can be conducted only if an efficient framework is available.Furthermore,informed decisions of the model/hardware’s overall performance rely on an adequate understanding of the global,not local,sensitivity of the individual design variables on the objectives.The surrogate-based approach,which involves approximating the objectives as continuous functions of design variables from limited data,offers a rational framework to reduce the number of important input variables,i.e.,the dimension of a design or modeling space.In this paper,we review the fundamental issues that arise in surrogate-based analysis and optimization,highlighting concepts,methods,techniques,as well as modeling implications for mechanics problems.To aid the discussions of the issues involved,we summarize recent efforts in investigating cryogenic cavitating flows,active flow control based on dielectric barrier discharge concepts,and lithium(Li)-ion batteries.It is also stressed that many multi-scale mechanics problems can naturally benefit from the surrogate approach for "scale bridging."     

Study of layered silicate clays as synergistic nucleating agent for polypropylene

Effect of very small quantities of organically modified layered silicate clay on the nucleation of polypropylene (PP), as an additive at ppm levels dosage was investigated, in combination with two of the most commercially exploited organic nucleating agents, one of which is a cyclic aromatic phosphinate salt and the other is bis(3,4‐dimethylbenzylidene) sorbitol, each representing a separate class of nucleating molecules by itself. Substitution of a considerable fraction of either of these organic nucleating agents with organically modified inorganic nanoclay was seen to result in a unique synergy between the two in nucleating PP. Polarized light microscopy studies of these synergistic formulations with organoclay to nucleating agent ratios of 1:1 and 1:3 totaling 0.2 weight percent in PP showed significant reduction in spherulite size from that of non‐nucleated PP, and compared with the samples containing exclusive organic nucleating agent at similar loading. Differential scanning calorimetric studies provided evidence and insight into such synergistic behavior. Crystallization and supercooling temperatures for the synergistic formulations were comparable for those formulations containing only organic nucleating agents, indicating comparable nucleation efficiency, whereas organoclay alone, although showing some extent of nucleation, was clearly poorer in efficiency. Wide and small angle X‐ray scattering studies further explained these observations. An increase in the gamma polytype fraction was seen in samples that contained both organoclay and nucleating agent, pointing to the role of organoclay as a gamma nucleator. Organoclay was found to be completely exfoliated in these synergistic formulations and was seen as well‐dispersed, single platelets in the PP matrix. A hybrid network consisting of exfoliated organoclay platelets and organic nucleating agent molecules was proposed, which is more stable and stiffer than the network formed by nucleating agent alone. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1786–1794, 2010     

Thiol–Ene “Click” Reaction Triggered by Neutral Ionic Liquid: The “Ambiphilic” Character of [hmim]Br in the Regioselective Nucleophilic Hydrothiolation

Thiol–ene “click” chemistry has emerged as a powerful strategy to construct carbon–heteroatom (C? S) bonds, which generally results in the formation of two regioisomers. To this end, the neutral ionic liquid [hmim]Br has been explored as a solvent cum catalyst for the synthesis of linear thioethers from activated and inactivated styrene derivatives or secondary benzyl alcohols and thiols without the requirement of using a metal complex, base, or free radical initiator. Furthermore, detailed mechanistic investigations using ¹H NMR spectroscopy and quadrupole time‐of‐flight electrospray ionization mass spectrometry (Q‐TOF ESI‐MS) revealed that the “ambiphilic” character of the ionic liquid promotes the nucleophilic addition of thiol to styrene through an anti‐Markovnikov pathway. The catalyst recyclability and the extension of the methodology for thiol–yne click chemistry are additional benefits. A competitive study among thiophenol, styrene, and phenyl acetylene revealed that the rate of reaction is in the order of thiol–yne>thiol–ene>dimerization of thiol in [hmim]Br.     

A numerical bifurcation study of friction effects in a slip-controlled torque converter clutch

Friction plays a key role in the efficiency and stability of the slip-controlled torque converter clutches. The effects of friction on the dynamics and stability of a slip-controlled torque converter clutch system using a bifurcation-analysis-based approach is presented in this paper. A three degree-of-freedom nonlinear driveline model with integral feedback action to control the clutch slip speed has been utilized for this study. The clutch interface friction is dependent on the slip speed and is a function of the static friction constant, μ ₀, the low velocity friction constant μ ₁, and the low velocity exponential rate, γ. Using one-parameter numerical continuation, local Hopf bifurcations of the subcritical type are observed as the friction parameters μ ₁ and γ were varied at low slip speeds. The continuation results are verified using simulations of the full nonlinear model. Stick-slip and undesirable oscillations of the model inertia elements are observed for certain parameter values. As the slip speed is increased, the bifurcation instability occurs at an increasingly higher value of μ ₁ signifying an improved tolerance of negative friction gradient at higher slip speeds. Smaller exponential rates γ are tolerated at higher slip speeds before the bifurcation instability occurs. For the range of parameter values considered, no bifurcations occur for a slip speeds higher than 3.4 and 4.5 rad/s with μ ₁ and γ as the continuation parameters, respectively. These values of slip speeds are much lower than the system’s first mode of torsional vibration of 16 Hz (≈100 rad/s).