Orientational melting and reorientational motion in a cubane molecular crystal: a molecular simulation study

Detailed molecular simulations are carried out to investigate the effect of temperature on orientational order in cubane molecular crystal. We report a transition from an orientationally ordered to an orientationally disordered plastic crystalline phase in the temperature range 425-450 K. This is similar to the experimentally reported transition at 395 K. The nature of this transition is first order and is associated with a 4.8% increase in unit cell volume that is comparable to the experimentally reported unit cell volume change of 5.4% (Phys. Rev. Lett. 1997, 78, 4938). An orientational order parameter, eta(T), has been defined in terms of average angle of libration of a molecular 3-fold axis and the orientational melting has been characterized by using eta(T). The orientational melting is associated with an anomaly in specific heat at constant pressure (C(P)) and compressibility (kappa). The enthalpy of transition and entropy of transition associated with this orientational melting are 20.8 J mol(-1) and 0.046 J mol(-1) K(-1), respectively. The structure of crystalline as well as plastic crystalline phases is characterized by using various radial distribution functions and orientational distribution functions. The coefficient of thermal expansion of the plastic crystalline phase is more than twice that of the crystalline phase.     

A numerical study of the target system of an ADSS with different flow guides

The mechanical design of the target module of an accelerator driven subcritical nuclear reactor system (ADSS) calls for an analysis of the related thermal-hydraulic issues because of large amount of heat deposition in the spallation region during the course of nuclear interactions with the molten lead bismuth eutectic (LBE) target. The LBE also should carry the entire heat generated as a consequence of the spallation reaction. The problem of heat removal by the LBE is a challenging thermal-hydraulic issue. For this, one has to examine the flows of low Prandtl number fluids (LBE) in a complex ADSS geometry. In this study, the equations governing the laminar flow and thermal energy are solved numerically using the streamline upwind Petrov-Galerkin (SUPG) finite element (FE) method. The target systems with a straight and a nozzle guide have been considered. The principal purpose of the analysis is to trace the flow and temperature distribution and thereby to check the suitability of the flow guide in avoiding the recirculation or stagnation zones in the flow space that may lead to hot spots.      

Pressure-induced ordering in adamantane: a Monte Carlo simulation study

Isothermal-isobaric ensemble Monte Carlo simulation of adamantane has been carried out with a variable shape simulation cell. The low-temperature crystalline phase and the room-temperature plastic crystalline phases have been studied employing the modified Williams potential. We show that at room temperature, the plastic crystalline phase transforms to the crystalline phase on increase in pressure. Further, we show that this is the same phase as the low-temperature ordered tetragonal phase of adamantane. The high-pressure ordered phase appears to be characterized by a slightly larger shift of the first peak toward a lower value of r in C-C, C-H, and H-H radial distribution functions as compared to the low-temperature tetragonal phase. The coexistence curve between the crystalline and plastic crystalline phase has been obtained approximately up to a pressure of 4 GPa.     

Spectral, optical, and thermal studies of pure and Zn(II)-doped l-histidine hydrochloride monohydrate (LHHC) crystals

The influence of doping the transition metal Zn(II) on the growth, spectral, optical, and thermal properties of l-histidine hydrochloride monohydrate (LHHC) crystals grown by slow solvent evaporation method has been investigated. Structural characterizations of the grown crystals were carried out by single crystal X-ray diffraction analysis and it shows slight structural changes as a result of doping. The FT-IR spectral study reveals the presence of various functional groups and confirms the slight distortion of the structure of the crystals due to doping. The energy dispersive X-ray analysis reveals the incorporation of Zn(II) in the crystalline matrix of LHHC crystal. The UV?CVis spectral study was carried out to analyze the optical transmittance of the grown crystals and found that the transmittance is very high in the visible and UV regions for both pure and doped crystals. The second harmonic generation (SHG) for the grown crystals was confirmed by Nd:YAG laser. The scanning electron microscopy reveals the presence of defect centers and crystal voids. The thermal stability and purity of the grown crystals were analyzed by thermogravimetry, differential thermal analysis, and differential scanning calorimetry techniques.     

Synthesis and spectral studies on some tetrahydrobenzoxanthen-11-ones: crystal and molecular structure of 9,9-dimethyl-12-(2-nitrophenyl)-8,9,10,12-tetrahydrobenzo[<Emphasis Type="Italic">a</Emphasis>]xanthen-11-one

A series of 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-ones have been synthesized by the multicomponent reaction (MCR) of β-naphthol, aryl aldehydes, and dimedone by using BF₃:OEt₂ as a catalyst. The derived compounds have been analyzed by IR, NMR (1D and 2D), and mass spectra. The single crystal X-ray structural analysis of 9,9-dimethyl-12-(2-nitrophenyl)-8,9,10,12-tetrahydrobenzo[a]-xanthen-11-one evidences the envelope conformation of the cyclohexane ring and the pyran ring tends to adopt flattened-boat conformation.     

A monopole mass filter with a hyperbolic V-shaped electrode

In this article we compare the classical monopole mass filter of von Zahn and the monopole mass filter with a hyperbolic V-shaped electrode. The experimental results and those of computer simulation for both mass spectrometers are presented. We show that the replacement of a conventional 90 degrees V-shaped electrode by an electrode with a hyperbolic profile substantially improves the peak shape of any given mass, and increases the mass resolution by a factor of 3-4 and the abundance sensitivity by a factor of 100. The potential of high analytical performance combined with electroforming techniques for electrode manufacture indicate future practical uses of such instruments. Copyright 1999 John Wiley & Sons, Ltd.     

Fragmentation of chitosan by ultrasonic irradiation

Kinetics of chitosan fragmentation by ultrasonic irradiation at frequency of 20 kHz, and the effects of experimental variables (power of ultrasound, chitosan concentration and solution temperature) on fragmentation were investigated. The kinetics studies were followed by measuring solution viscosity of the original and its fragments, and determining average number of chain scission of the fragments. The effects of ultrasonic power, chitosan concentration and solution temperature on fragmentation process were followed by viscometry and size exclusion chromatography. The chemical structure of the original chitosan and its fragments were examined by (1)H NMR spectroscopy and elemental analysis. The experimental results showed that the rate of fragmentation increased with an increase in power of ultrasound. Chain scission increased with an increase in power of ultrasound; and solution temperature, but a decrease in chitosan concentration. The chemical structure and polydispersity of the original and the fragments were nearly identical. A model based on experimental data to describe the relationship between chain scission and experimental variables (power of ultrasound; irradiation time; reduced concentration, c[eta]; and solution temperature) was proposed. It was concluded that ultrasonic irradiation is a suitable method to perform partial depolymerization and to obtain moderate macromolecules from large ones.     

One-pot synthesis of Claisen–Schmidt reaction through (E)-chalcone derivatives: Spectral studies in human serum albumin protein binding and molecular docking investigation

An efficient and environmentally benign one-pot multicomponent synthesis of E-chalcones was developed using a mild and reusable new boron nitride-sulphonic acid catalyst. The catalyst was prepared by activating the boron nitride surface with nitric acid, followed by a simple reaction with 3-mercaptopropyl trimethoxysilane. The catalyst was characterized and morphological properties were studied by Fourier transform infrared, X-ray diffraction, transmission electron spectroscopy, scanning electron microscopy, Brunauer–Emmett–Teller theory, and Raman spectroscopy techniques. The solid acid catalyst was recycled five times in a Claisen–Schmidt reaction to synthesize new chalcone derivatives, and X-ray crystallography was used to elucidate the structure of (E)-1-(anthracen-9-yl)-3-(2-(4-methylpiperazin-1-yl)quinolin-3-yl)prop-2-en-1-one. A fluorescence quench titration method was used to assess its binding ability with human serum albumin (HSA), while molecular docking was also performed to get a more detailed insight into their interaction at the binding site of HSA.     

A second-order splitting combined with orthogonal cubic spline collocation method for the Rosenau equation

A second-order splitting method is applied to a KdV-like Rosenau equation in one space variable. Then an orthogonal cubic spline collocation procedure is employed to approximate the resulting system. This semidiscrete method yields a system of differential algebraic equations (DAEs) of index 1. Error estimates in L² and L^∞ norms have been obtained for the semidiscrete approximations. For the temporal discretization, the time integrator RADAU5 is used for the resulting system. Some numerical experiments have been conducted to validate the theoretical results and to confirm the qualitative behaviors of the Rosenau equation. Finally, orthogonal cubic spline collocation method is directly applied to BBM (Benjamin–Bona–Mahony) and BBMB (Benjamin–Bona–Mahony–Burgers) equations and the well-known decay estimates are demonstrated for the computed solution. © 1998 John Wiley & Sons, Inc. Numer Methods Partial Differential Eq 14: 695–716, 1998