Thermal reactivity of poly(styrene peroxide): a thermodynamic approach

Abstract is not available.

Compressible boundary-layer flow at a three-dimensional stagnation point with massive blowing

The effect of massive blowing rates on the steady laminar compressible boundary-layer flow with variable gas properties at a 3-dim. stagnation point (which includes both nodal and saddle points of attachment) has been studied. The equations governing the flow have been solved numerically using an implicit finite-difference scheme in combination with the quasilinearization technique for nodal points of attachment but employing a parametric differentiation technique instead of quasilinearization for saddle points of attachment. It is found that the effect of massive blowing rates is to move the viscous layer away from the surface. The effect of the variation of the density- viscosity product across the boundary layer is found to be negligible for massive blowing rates but significant for moderate blowing rates. The velocity profiles in the transverse direction for saddle points of attachment in the presence of massive blowing show both the reverse flow as well as velocity overshoot.

Coalescence of rigid droplets in a stirred dispersion-II. Band-limited force fluctuations

The coalescence of nearly rigid liquid droplets in a turbulent flow field is viewed as the drainage of a thin film of liquid under the action of a stochastic force representing the effect of turbulence. The force squeezing the drop pair is modelled as a correlated random function of time. The drops are assumed to coalesce once the film thickness becomes smaller than a critical thickness while they are regarded as separated if their distance of separation is larger than a prescribed distance. A semi-analytical solution is derived to determine the coalescence efficiency. The veracity of the solution procedure is established via a Monte-Carlo solution scheme. The model predicts a reversing trend of the dependence of the coalescence efficiency on the drop radii, the film liquid viscosity and the turbulence energy dissipation per unit mass, as the relative fluctuation increases. However, the dependence on physical parameters is weak (especially at high relative fluctuation) so that for the smallest droplets (which are nearly rigid) the coalescence efficiency may be treated as an empirical constant. The predictions of this model are compared with those of a white-noise force model. The results of this paper and those in Muralidhar and Ramkrishna (1986, Ind. Engng Chem. Fundam. 25, 554-56) suggest that dynamic drop deformation is the key factor that influences the coalescence efficiency.

A Raman study of multiferroic LuMnO3

Magnetic and dielectric measurements confirm the multiferroic nature of LuMnO3. Raman spectra of LuMnO3 have been recorded in the 77-800 K range covering both the antiferromagnetic transition at 90 K and the ferroelectric-paraelectric transition at 750 K. The changes in the phonon modes frequencies and band-widths indicate the presence of phonon-spin coupling in the antiferromagnetically ordered phase. The ferroelectric-paraelectric transition is accompanied by the broadening and disappearance of many of the phonon modes. Some of the phonon modes also show anomalies at the ferroelectric transition.

Theoretical calculations of base-base interactions in nucleic acids: I Stacking interactions in free bases

Stacking interactions in free bases were computed on the basis of molecular association. The results of the calculations were compared with the stacking patterns observed in a few single crystals of nucleic acid components as examples. The following are the conclusions: (i) there can be two types of stacking pattern classified as normal and inverted types for any two interacting bases and both can be energetically favourable (ii) in both the types the stacking interaction is a combined effect of the overlap of the interacting bases and relative positions and orientations of the atomic centres of the two bases (iii) crystal symmetry and H-bonding interaction may influence stacking patterns.

Gabapentin: A Stereochemically Constrained gamma Amino Acid Residue in Hybrid Peptide Design

Nature has used the all-alpha-polypeptide backbone of proteins to create a remarkable diversity of folded structures. Sequential patterns of 20 distinct amino adds, which differ only in their side chains, determine the shape and form of proteins. Our understanding of these specific secondary structures is over half a century old and is based primarily on the fundamental elements: the Pauling alpha-helix and beta-sheet. Researchers can also generate structural diversity through the synthesis of polypeptide chains containing homologated (omega) amino acid residues, which contain a variable number of backbone atoms. However, incorporating amino adds with more atoms within the backbone introduces additional torsional freedom into the structure, which can complicate the structural analysis. Fortunately, gabapentin (Gpn), a readily available bulk drug, is an achiral beta,beta-disubstituted gamma amino add residue that contains a cyclohexyl ring at the C-beta carbon atom, which dramatically limits the range of torsion angles that can be obtained about the flanking C-C bonds. Limiting conformational flexibility also has the desirable effect of increasing peptide crystallinity, which permits unambiguous structural characterization by X-ray diffraction methods. This Account describes studies carried out in our laboratory that establish Gpn as a valuable residue in the design of specifically folded hybrid peptide structures. The insertion of additional atoms into polypeptide backbones facilitates the formation of intramolecular hydrogen bonds whose directionality is opposite to that observed in canonical alpha-peptide helices. If hybrid structures mimic proteins and biologically active peptides, the proteolytic stability conferred by unusual backbones can be a major advantage in the area of medicinal chemistry. We have demonstrated a variety of internally hydrogen-bonded structures in the solid state for Gpn-containing peptides, including the characterization of the C-7 and C-9 hydrogen bonds, which can lead to ribbons in homo-oligomeric sequences. In hybrid alpha gamma sequences, district C-12 hydrogen-bonded turn structures support formation of peptide helices and hairpins in longer sequences. Some peptides that include the Gpn residue have hydrogen-bond directionality that matches alpha-peptide helices, while others have the opposite directionality. We expect that expansion of the polypeptide backbone will lead to new classes of foldamer structures, which are thus far unknown to the world of alpha-polypeptides. The diversity of internally hydrogen-bonded structures observed in hybrid sequences containing Gpn shows promise for the rational design of novel peptide structures incorporating hybrid backbones.

Crystallization and Preliminary X-ray Studies of the Basic Lectin from Winged Bean (Psophocarpus tetragonolobus)

The basic lectin from winged bean (Psophocarpus tetragonolobus) could be crystallized using polyethyleneglycol (PEG) 4000 (I), PEG 8000 (II) and 2-methylpentane-2,4-diol (MPD) (III) as precipitants. Crystal forms I and II grew in the presence of methyl-α-Image -galactopyranoside or N -acetylgalactosamine while III grew in the absence of sugar. The three forms have the same space group (P21212) and similar unit cell dimensions with two dimeric molecules in the asymmetric unit. The unit cell dimensions are a = 156·8 Å, b = 89·0 Å, c = 73·3 Å for I, a = 155·5 Å, b = 92·3 Å, c = 72·5 Å for II and a = 148·3 Å, b = 90·7 Å, c = 73·8 Å for III. The crystals, particularly those grown using PEG 8000, are suitable for high resolution X-ray analysis, which is in progress.

Generalised vortex motion of compressible fluid with and without magnetic field and suction

The laminar boundary layer over a stationary infinite disk induced by a rotating compressible fluid is considered. The free stream velocity has been taken as tangential and varies as a power of radius, i.e. v∞ ˜ r−n. The effect of the axial magnetic field and suction is also included in the analysis. An implicit finite difference scheme is employed to the governing similarity equations for numerical computations. Solutions are studied for various values of disk to fluid temperature ratio and for values of n between 1 and −1. In the absence of the magnetic field and suction, velocity profiles exhibit oscillations. It has been observed that for a hot disk in the presence of a magnetic field the boundary layer solutions decay algebraically instead of decaying exponentially. In the absence of the magnetic field and suction, the solution of the similarity equations exists only for a certain range of n.

Structure of 5-methyl-2'-deoxycytidine 5'-monophosphate dihydrate

CloHI6N307P.2H20 , Mr = 357.2, triclinic, P1, a = 4-8520 (8), b = 8"3703 (8), c = 10.0199 (12) A, a= 104.578 (9),/3= 102.332 (13), 7=93.670(11) o, V = 381"75 A 3, Z = 1, Dx = 1"55, Dm = 1"53 Mg m -3, a(Cu Ka) = 1.5418 A,/z = 2.01 mm- l, F(000) = 188, T= 290 K, R = 0-049 for 1568 unique reflections.

Hydrothermal synthesis, characterization and Raman studies of Eu3+ activated Gd2O3 nanorods

Eu3+ (8 mol%) activated gadolinium oxide nanorods have been prepared by hydrothermal method without and with surfactant, cityl trimethyl ammonium bromide (CTAB). Powder X-ray diffraction (PXRD) studies reveal that the as-formed product is in hexagonal Gd(OH)(3):Eu phase and subsequent heat treatment at 350 and 600 degrees C transforms the sample to monoclinic GdOOH:Eu and cubic Gd2O3:Eu phases, respectively. The structural data and refinement parameters for cubic Gd2O3:Eu nanorods were calculated by the Rietveld refinement. SEM and TEM micrographs show that as-obtained Gd(OH)(3):Eu consists of uniform nanorods in high yield with uniform diameters of about 15 nm and lengths of about 50-150 nm. The temperature dependent morphological evolution of Gd2O3:Eu without and with CTAB surfactant was studied. FTIR studies reveal that CTAB surfactant plays an important role in converting cubic Gd2O3:Eu to hexagonal Gd(OH)(3):Eu. The strong and intense Raman peak at 489 cm(-1) has been assigned to A(g) mode, which is attributed to the hexagonal phase of Gd2O3. The peak at similar to 360 cm(-1) has been assigned to the combination of F-g and E-g modes, which is mainly attributed to the cubic Gd2O3 phase. The shift in frequency and broadening of the Raman modes have been attributed to the decrease in crystallite dimension to the nanometer scale as a result of phonon confinement. (C) 2010 Elsevier B.V. All rights reserved.

Homogenization of periodic structures via Bloch decomposition

In this paper, the classical problem of homogenization of elliptic operators in arbitrary domains with periodically oscillating coefficients is considered. Using Bloch wave decomposition, a new proof of convergence is furnished. It sheds new light and offers an alternate way to view the classical results. In a natural way, this method leads us to work in the Fourier space and thus in a framework dual to the one used by L. Tartar [Problemes d'Homogeneisation dans les Equations aux: Derivees Partielles, Cours Peccot au College de Prance, 1977] in his method of homogenization. Further, this technique offers a nontraditional way of calculating the homogenized coefficients which is easy to implement in the computer.

Temperature dependence of infrared and Raman modes in polymeric RbC60

Temperature dependence of the intra-molecular vibrational modes Of C-60 in the quasi-1D polymeric RbC60, across the low temperature transition at similar to50 K, has been probed through infrared (IR) and Raman spectroscopies. With the lowering of temperature, the split IR modes of RbC60 are seen to harden but below 50 K a small but definitive signature of an anomalous softening is observed. In addition, the background IR transmission shows an increase below 50 K with the opening of a well defined gap in the electronic spectrum. The implications of these results, along with those of Raman measurements, are discussed in terms of the interaction of intra-molecular phonons with electrons and spin excitations in the system. (C) 2002 Published by Elsevier Science Ltd.

Constructing a wire-frame from views on arbitrary view planes for objects with conic sections inclined to all view planes

A new and efficient approach to construct a 3D wire-frame of an object from its orthographic projections is described. The input projections can be two or more and can include regular and complete auxiliary views. Each view may contain linear, circular and other conic sections. The output is a 3D wire-frame that is consistent with the input views. The approach can handle auxiliary views containing curved edges. This generality derives from a new technique to construct 3D vertices from the input 2D vertices (as opposed to matching coordinates that is prevalent in current art). 3D vertices are constructed by projecting the 2D vertices in a pair of views on the common line of the two views. The construction of 3D edges also does not require the addition of silhouette and tangential vertices and subsequently splitting edges in the views. The concepts of complete edges and n-tuples are introduced to obviate this need. Entities corresponding to the 3D edge in each view are first identified and the 3D edges are then constructed from the information available with the matching 2D edges. This allows the algorithm to handle conic sections that are not parallel to any of the viewing directions. The localization of effort in constructing 3D edges is the source of efficiency of the construction algorithm as it does not process all potential 3D edges. Working of the algorithm on typical drawings is illustrated. (C) 2011 Elsevier Ltd. All rights reserved.

Adaptation of small capacity natural gas engine for producer gas operation

This article addresses the adaptation of a low-power natural gas engine for using producer gas as a fuel. The 5.9 L natural gas engine with a compression ratio of 10.5:1, rated at 55 kW shaft power, delivered 30 kW using producer gas as fuel in the naturally aspirated mode. Optimal ignition timing for peak power was found to be 20 degrees before top dead centre. Air-to-fuel ratio (A/F) was found to be 1.2 +/- 0.1 over a range of loads. Critical evaluation of the energy flows in the engine resulted in identifying losses and optimizing the engine cooling. The specific fuel consumption was found to be 1.2 +/- 0.1 kg of biomass per kilowatt hour. A reduction of 40 per cent in brake mean effective pressure was observed compared with natural gas operation. Governor response to load variations has been studied with respect to frequency recovery time. The study also attempts to adopt a turbocharger for higher power output. Preliminary results suggest a possibility of about 30 per cent increase in the output.

Averting biodiversity collapse in tropical forest protected areas

The rapid disruption of tropical forests probably imperils global biodiversity more than any other contemporary phenomenon(1-3). With deforestation advancing quickly, protected areas are increasingly becoming final refuges for threatened species and natural ecosystem processes. However, many protected areas in the tropics are themselves vulnerable to human encroachment and other environmental stresses(4-9). As pressures mount, it is vital to know whether existing reserves can sustain their biodiversity. A critical constraint in addressing this question has been that data describing a broad array of biodiversity groups have been unavailable for a sufficiently large and representative sample of reserves. Here we present a uniquely comprehensive data set on changes over the past 20 to 30 years in 31 functional groups of species and 21 potential drivers of environmental change, for 60 protected areas stratified across the world's major tropical regions. Our analysis reveals great variation in reserve `health': about half of all reserves have been effective or performed passably, but the rest are experiencing an erosion of biodiversity that is often alarmingly widespread taxonomically and functionally. Habitat disruption, hunting and forest-product exploitation were the strongest predictors of declining reserve health. Crucially, environmental changes immediately outside reserves seemed nearly as important as those inside in determining their ecological fate, with changes inside reserves strongly mirroring those occurring around them. These findings suggest that tropical protected areas are often intimately linked ecologically to their surrounding habitats, and that a failure to stem broad-scale loss and degradation of such habitats could sharply increase the likelihood of serious biodiversity declines.