Nanocrystals,Nanorods and other Nanostructures of Nickel,Ruthenium, Rhodium and Iridium prepared by a Simple Solvothermal Procedure

The solvothermal decomposition of nickel acetate in n-octylamine medium at 250 °C gives rise to nickel nanostructures while in a hydrocarbon medium NiO nanostructures are obtained. It has been possible to obtain nickel nanorods of 12–15 nm diameter by this means. By carrying out the reaction at a slightly higher temperature, ultra-thin single-crystalline sheets of nickel are obtained. The nanorods and the thin sheets, with the FCC structure, are both ferromagnetic at room temperature, with the nanorods exhibiting high coercivities. It has been possible to obtain ruthenium, rhodium and iridium nanostructures by carrying out the decomposition of the respective metal acetylacetonates in a hydrocarbon (decalin or toluene) or an amine (n-octylamine or oleylamine) around 300 °C. Nanorod formation is favored by linear long-chain amines. The method described by us to prepare the nanostructures of nickel, ruthenium, rhodium and iridium is simple and straightforward compared to the literature procedures, the preparation of single-crystalline thin sheets of nickel by such a solution route being noteworthy. The nanostructures prepared in the amine media could be readily dispersed in hydrocarbon solvents. Dedicated to Professor Dr. Günther Schmid     

Nonlinear Longitudinal Vibrations of Transversally Polarized Piezoceramics: Experiments and Modeling

Nonlinear behavior of piezoceramics at strong electric fields is a well-known phenomenon and is described by various hysteresis curves. On the other hand, nonlinear vibration behavior of piezoceramics at weak electric fields has recently been attracting considerable attention. Ultrasonic motors (USM) utilize the piezoceramics at relatively weak electric fields near the resonance. The consistent efforts to improve the performance of these motors has led to a detailed investigation of their nonlinear behavior. Typical nonlinear dynamic effects can be observed, even if only the stator is experimentally investigated. At weak electric fields, the vibration behavior of piezoceramics is usually described by constitutive relations linearized around an operating point. However, in experiments at weak electric fields with longitudinal vibrations of piezoceramic rods, a typical nonlinear vibration behavior similar to that of the USM-stator is observed at near-resonance frequency excitations. The observed behavior is that of a softening Duffing-oscillator, including jump phenomena and multiple stable amplitude responses at the same excitation frequency and voltage. Other observed phenomena are the decrease of normalized amplitude responses with increasing excitation voltage and the presence of superharmonics in spectra. In this paper, we have attempted to model the nonlinear behavior using higher order (quadratic and cubic) conservative and dissipative terms in the constitutive equations. Hamilton's principle and the Ritz method is used to obtain the equation of motion that is solved using perturbation techniques. Using this solution, nonlinear parameters can be fitted from the experimental data. As an alternative approach, the partial differential equation is directly solved using perturbation techniques. The results of these two different approaches are compared.     

Calculation of overall heat transfer coefficients in a triple tube heat exchanger

In previous studies, calculation of overall heat transfer coefficients in a triple tube heat exchanger (TTHE) involved assumptions or approaches those are not valid in all cases. In this study a more generic way of calculating overall heat transfer coefficients in a TTHE has been developed. Consequently, temperature profiles of all streams in a TTHE in the axial direction were determined. An effective overall heat transfer coefficient that is related to the total resistance to heat transfer in the TTHE, was also determined to facilitate comparison of a TTHE to an equivalent double tube heat exchanger.     

Raman imaging and stress quantification in self‐assembled graphene oxide fiber ‘Latin Letters’

To probe the intrinsic stress distribution in terms of spatial Raman shift (ω) and change in the phonon linewidth (Γ), here we analyze self‐assembled graphene oxide fibers (GOF) ‘Latin letters’ by confocal Raman spectroscopy. The self‐assembly of GOF ‘Latin letters’ has been explained through surface tension, π–π stacking, van der Waals interaction at the air–water interface and by systematic time‐dependent investigation using field emission scanning electron microscopy analysis. Intrinsic residual stress due to structural joints and bending is playing a distinct role affecting the E_2g mode (G band) at and away from the physical interface of GOF segments with broadening of phonon linewidth, indicating prominent phonon softening. Linescan across an interface of the GOF ‘letters’ reveals Raman shift to lower wavenumber in all cases but more so in ‘Z’ fiber exhibiting a broader region. Furthermore, intrinsic stress homogeneity is observed for ‘G’ fiber distributed throughout its curvature with negligible shift corresponding to E_2g mode vibration. This article demonstrates the significance of morphology in stress distribution across the self‐assembled and ‘smart‐integrable’ GOF ‘Latin letters’. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis of RE Y zeolite for formulation of FCC catalyst and the catalytic performance in cracking of n-hexadecane

Research on Chemical Intermediates - This study presents the synthesis of rare earth-doped Y (RE Y) zeolite, its application in formulation of a fluid catalytic cracking (FCC) catalyst and the...     

Effect of zeolite pore morphology on solvent-less alkylation of benzene with 1-hexene

In an attempt to convert the carcinogenic benzene which is almost restricted for its use in gasoline, alkylation reaction with olefin 1-hexene has been conducted on various zeolites. Four zeolites having different pore topology and pore size have been applied as solid acid catalysts for effective production of alkylate in a liquid phase, solvent-less low temperature reaction. The textural properties of all the four zeolites (ZSM-5, MOR, BEA, HY) have been characterized for crystal morphology by TEM, crystal structure by XRD and FTIR, BET for surface area, N₂ sorption for porosity and TPD for acidity. Among the zeolite, BEA possessed high surface area (600.61 m²/g) and enhanced meso pores volume (0.3956 cm³/g) as compared to other zeolite samples. The performance of BEA was also observed to be superior in the liquid phase alkylation of benzene with 1-hexene in a batch reactor under autogenous pressure without using any solvent. At the optimum reaction conditions, the benzene conversion was 86.6 wt% and 3-Phenylhexane, 2-Phenylhexane yield were about 47.9 wt% and 38.7 wt% respectively on this catalyst. The BEA also exhibited longer time-on-stream and reusability performance, thus offers an attractive route for converting benzene into valuable (3-Phenylhexane, 2-Phenylhexane) alkylate product useful for the manufacturing of fine chemicals, dyestuff, detergents and scents.     

Multiple Response Optimization of a HPLC Method for the Determination of Enantiomeric Purity of S-Ofloxacin

The aim of the study was to develop a new HPLC method for direct chiral separation of Ofloxacin enantiomers using polar non-aqueous mobile phase by application of response surface methodology. Rotatable central composite design (CCD) with eight factorial points, six axial points and six replications in central point was used to evaluate the influence of three independent variables (concentration of methanol, diethylamine and flow rate) on the output responses (capacity factor of first peak, tailing factors of both the enantiomers, resolution between the Ofloxacin enantiomers, retention time of the last peak and chromatographic optimization function). Further, CCD data were combined with multiple response optimization in order to obtain a set of optimal experimental conditions (% methanol/hexane/acetonitrile-43.33/10/46.62 (v/v), % acetic acid/diethylamine-0.4/0.2 and flow rate as 1.4 mL min^?1) leading to the most desirable compromise between resolution and analysis time. The method demonstrated good correlation between observed and predicted responses. The developed method was validated according to ICH guidelines and applied for quantitative analysis of two commercially available tablets Zenoflox (Ofloxacin) and Glevo (Levofloxacin). Good agreement was found between the assay results and the label claim of the marketed formulations by showing good %recovery and %CV. The study resulted in a better chromatographic system for the determination of Ofloxacin enantiomers.     

Structural, dynamic, and electrostatic properties of fully hydrated DMPC bilayers from molecular dynamics simulations accelerated with graphical processing units (GPUs)

We present results of molecular dynamics simulations of fully hydrated DMPC bilayers performed on graphics processing units (GPUs) using current state-of-the-art non-polarizable force fields and a local GPU-enabled molecular dynamics code named FEN ZI. We treat the conditionally convergent electrostatic interaction energy exactly using the particle mesh Ewald method (PME) for solution of Poisson's Equation for the electrostatic potential under periodic boundary conditions. We discuss elements of our implementation of the PME algorithm on GPUs as well as pertinent performance issues. We proceed to show results of simulations of extended lipid bilayer systems using our program, FEN ZI. We performed simulations of DMPC bilayer systems consisting of 17,004, 68,484, and 273,936 atoms in explicit solvent. We present bilayer structural properties (atomic number densities, electron density profiles), deuterium order parameters (S(CD)), electrostatic properties (dipole potential, water dipole moments), and orientational properties of water. Predicted properties demonstrate excellent agreement with experiment and previous all-atom molecular dynamics simulations. We observe no statistically significant differences in calculated structural or electrostatic properties for different system sizes, suggesting the small bilayer simulations (less than 100 lipid molecules) provide equivalent representation of structural and electrostatic properties associated with significantly larger systems (over 1000 lipid molecules). We stress that the three system size representations will have differences in other properties such as surface capillary wave dynamics or surface tension related effects that are not probed in the current study. The latter properties are inherently dependent on system size. This contribution suggests the suitability of applying emerging GPU technologies to studies of an important class of biological environments, that of lipid bilayers and their associated integral membrane proteins. We envision that this technology will push the boundaries of fully atomic-resolution modeling of these biological systems, thus enabling unprecedented exploration of meso-scale phenomena (mechanisms, kinetics, energetics) with atomic detail at commodity hardware prices.     

Temperature- and pH-responsive self-assembly of poly(propylene oxide)-b-poly(lysine) block copolymers in aqueous solution

A series of poly(propylene oxide)-b-poly(L-lysine) (PPO-PK) block copolymers were synthesized using Huisgen's 1,3-dipolar cycloaddition, and the solution self-assembly was studied using transmission electron microscopy, circular dichroism spectroscopy, and dynamic and static light scattering techniques. In contrast to previous studies of poly(lysine)-based block copolymers, PPO-PK exhibits a significant shift in the pH associated with the helix-coil transition of the poly(lysine) block, potentially a result of decreased hydrophobicity in the core PPO block. Given the proximity of the lower critical solution temperature of the PPO block, these materials exhibit both pH and temperature-responsive (i.e., "schizophrenic") self-assembly, the latter of which was interpreted in terms of changes in the second osmotic virial coefficient. Finally, the vesicle morphology obtained from these polymers was studied for the propensity in drug encapsulation and passive release.