Mass spectrometric study of the dissociation of Group XI metal complexes with fatty acids and glycerolipids : Ag2H+ and Cu2H+ ion formation in the presence of a double bond

Results of mass spectrometric studies are reported for the collisional dissociation of Group XI (Cu, Ag, Au) metal ion complexes with fatty acids (palmitic, oleic, linoleic and a-linolenic) and glycerolipids. Remarkably, the formation of M2H+ ions (M = Cu, Ag) is observed as a dissociation product of the ion complexes containing more than one metal cation and only if the lipid in the complex contains a double bond. Ag2H+ is formed as the main dissociation channel for all three of the fatty acids containing double bonds that were investigated while Cu2H+ is formed with one of the fatty acids and, although abundant, is not the dominant dissociation channel. Also. Cu(I) and Ag(I) ion complexes were observed with glycerolipids (including triacylglycerols and glycerophospholipids) containing either saturated or unsaturated fatty acid substituents. Interestingly. Ag2H+ ion is formed in a major fragmentation channel with the lipids that are able to form the complex with two metal cations (triacylglycerols and glycerophosphoglycerols), while lipids containing a fixed positive charge (glycerophospocholines) complex only with a single metal cation. The formation of Ag2H+ ion is a significant dissociation channel from the complex ion Ag-2(L-H)(+) where L = Glycerophospholipid (GP) (18:1/18:1). Cu(I) also forms complexes of two metal cations with glycerophospholipids but these do not produce Cu2H+ upon dissociation. Rather organic fragments, not containing Cu(I), are formed, perhaps due to different interactions of these metal cations with lipids resulting from the much smaller ionic radius of Cu(I) compared to Ag(I) (C).

Plasma-assisted self-sharpening of platelet-structured single-crystalline carbon nanocones

A mechanism and model for the vertical growth of platelet-structured vertically aligned single-crystalline carbon nanostructures by the formation of graphene layers on a flat top surface are proposed and verified experimentally. It is demonstrated that plasma-related effects lead to self-sharpening of tapered nanocones to form needlelike nanostructures, in a good agreement with the predicted dependence of the radius of a nanocone's flat top on the incoming ion flux and surface temperature. The growth mechanism is relevant to a broad class of nanostructures including nanotips, nanoneedles, and nanowires and can be used to improve the predictability of nanofabrication processes. © 2007 American Institute of Physics.

Angular distribution of carbon ion flux in a nanotube array during the plasma process by the Monte Carlo technique

Angular distribution of microscopic ion fluxes around nanotubes arranged into a dense ordered pattern on the surface of the substrate is studied by means of multiscale numerical simulation. The Monte Carlo technique was used to show that the ion current density is distributed nonuniformly around the carbon nanotubes arranged into a dense rectangular array. The nonuniformity factor of the ion current flux reaches 7 in dense (5× 1018 m-3) plasmas for a nanotube radius of 25 nm, and tends to 1 at plasma densities below 1× 1017 m-3. The results obtained suggest that the local density of carbon adatoms on the nanotube side surface, at areas facing the adjacent nanotubes of the pattern, can be high enough to lead to the additional wall formation and thus cause the single- to multiwall structural transition, and other as yet unexplained nanoscience phenomena.

Total factor productivity growth and convergence in the petroleum industry : empirical analysis testing for convexity

While economic theory acknowledges that some features of technology (e.g., indivisibilities, economies of scale and specialization) can fundamentally violate the traditional convexity assumption, almost all empirical studies accept the convexity property on faith. In this contribution, we apply two alternative flexible production technologies to measure total factor productivity growth and test the significance of the convexity axiom using a nonparametric test of closeness between unknown distributions. Based on unique field level data on the petroleum industry, the empirical results reveal significant differences, indicating that this production technology is most likely non-convex. Furthermore, we also show the impact of convexity on answers to traditional convergence questions in the productivity growth literature.

Oldest pathology in a tetrapod bone illuminates the origin of terrestrial vertebrates

The origin of terrestrial tetrapods was a key event in vertebrate evolution, yet how and when it occurred remains obscure, due to scarce fossil evidence. Here, we show that the study of palaeopathologies, such as broken and healed bones, can help elucidate poorly understood behavioural transitions such as this. Using high-resolution finite element analysis, we demonstrate that the oldest known broken tetrapod bone, a radius of the primitive stem tetrapod Ossinodus pueri from the mid-Viséan (333 million years ago) of Australia, fractured under a high-force, impact-type loading scenario. The nature of the fracture suggests that it most plausibly occurred during a fall on land. Augmenting this are new osteological observations, including a preferred directionality to the trabecular architecture of cancellous bone. Together, these results suggest that Ossinodus, one of the first large (>2m length) tetrapods, spent a significant proportion of its life on land. Our findings have important implications for understanding the temporal, biogeographical and physiological contexts under which terrestriality in vertebrates evolved. They push the date for the origin of terrestrial tetrapods further back into the Carboniferous by at least two million years. Moreover, they raise the possibility that terrestriality in vertebrates first evolved in large tetrapods in Gondwana rather than in small European forms, warranting a re-evaluation of this important evolutionary event.

Morphometric analysis of the thoracic intervertebral foramen osseous anatomy in adolescent idiopathic scoliosis using low dose computerized tomography

Introduction. The dimensions of the thoracic intervertebral foramen in adolescent idiopathic scoliosis (AIS) have not previously been quantified. During posterior approach scoliosis correction surgery pedicle screws may occasionally breach into the foramen. Better understanding of the dimensions of the foramen may be useful in surgical planning. This study describes a reproducible method for measurement of the thoracic foramen in AIS using computerized tomography (CT). Methods. In 23 pre-operative female patients with Lenke 1 type AIS with right side convexity major curves confined to the thoracic spine the foraminal height (FH), foraminal width (FW), pedicle to superior articular process distance (P-SAP) and cross sectional foraminal area (FA) were measured using multiplanar reconstructed CT. Measurements were made at entrance, midpoint and exit of the thoracic foramina from T1/T2 to T11/T12. Results were correlated with potential dependent variables of major curve Cobb Angle measured on X-ray and CT, Age, Weight, Lenke classification subtype, Risser Grade and number of spinal levels in the major curve. Results. The FH, FW, P-SAP and FA dimensions and ratios are all significantly larger on the convexity of the major curve and maximal at or close to the apex. Mean thoracic foraminal dimensions change in a predictable manner relative to position on the major thoracic curve. There was no significant correlation with the measured foraminal dimensions or ratios and the potential dependent variables. The average ratio of convexity to concavity dimensions at the apex foramina for entrance, midpoint and exit respectively are FH (1.50, 1.38, 1.25), FW (1.28, 1.30, 0.98), FA (2.06, 1.84, 1.32), P-SAP (1.61, 1.47, 1.30). Conclusion. Foraminal dimensions of the thoracic spine are significantly affected by AIS. Foraminal dimensions have a predictable convexity to concavity ratio relative to the proximity to the major curve apex. Surgeons should be aware of these anatomical differences during scoliosis correction surgery.

The impact of orbital errors on the estimation of satellite clock errors and PPP

Precise satellite orbit and clocks are essential for providing high accuracy real-time PPP (Precise Point Positioning) service. However, by treating the predicted orbits as fixed, the orbital errors may be partially assimilated by the estimated satellite clock and hence impact the positioning solutions. This paper presents the impact analysis of errors in radial and tangential orbital components on the estimation of satellite clocks and PPP through theoretical study and experimental evaluation. The relationship between the compensation of the orbital errors by the satellite clocks and the satellite-station geometry is discussed in details. Based on the satellite clocks estimated with regional station networks of different sizes (∼100, ∼300, ∼500 and ∼700 km in radius), results indicated that the orbital errors compensated by the satellite clock estimates reduce as the size of the network increases. An interesting regional PPP mode based on the broadcast ephemeris and the corresponding estimated satellite clocks is proposed and evaluated through the numerical study. The impact of orbital errors in the broadcast ephemeris has shown to be negligible for PPP users in a regional network of a radius of ∼300 km, with positioning RMS of about 1.4, 1.4 and 3.7 cm for east, north and up component in the post-mission kinematic mode, comparable with 1.3, 1.3 and 3.6 cm using the precise orbits and the corresponding estimated clocks. Compared with the DGPS and RTK positioning, only the estimated satellite clocks are needed to be disseminated to PPP users for this approach. It can significantly alleviate the communication burdens and therefore can be beneficial to the real time applications.

Stability of Dimeric Interface in Banana Lectin: Insight from Molecular Dynamics Simulations

Banana lectin (Banlec) is a homodimeric non-glycosylated protein. It exhibits the b-prism I structure. High-temperature molecular dynamics simulations have been utilized to monitor and understand early stages of thermally induced unfolding of Banlec. The present study elucidates the behavior of the dimeric protein at four different temperatures and compares the structural and conformational changes to that of the minimized crystal structure. The process of unfolding was monitored by following the radius of gyration, the rms deviation of each residue, change in relative solvent accessibility and the pattern of inter- and intra-subunit interactions. The overall study demonstrates that the Banlec dimer is a highly stable structure, and the stability is mostly contributed by interfacial interactions. It maintains its overall conformation during high-temperature (400–500 K) simulations, with only the unstructured loop regions acquiring greater momentum under such condition. Nevertheless, at still higher temperatures (600 K) the tertiary structure is gradually lost which later extends to loss of secondary structural elements. The pattern of hydrogen bonding within the subunit and at the interface across different stages has been analyzed and has provided rationale for its intrinsic high stability.

Analysis Of Curved Laminated Beams Of Bimodulus Composite-Materials

Composite materials exhibiting different moduli in tension and in compression, commonly called as bimodular composites are being used in many engineering fields. A finite element analysis is carried out for small deflection static behavior of laminated curved beams of bi modulus materials for both solid and hollow circular cross-sections using an iterative procedure. The finite element has 16 d.o.f. and uses the displacement field in terms of first order Hermite in terpolation polynomials. The neutral surface, i.e. the locus of points having zero axial strain is found to vary drastically depending on the loading, lay up schemes and radius of curvature. As il lustrations, plots of the cross-sections of the ruled neutral-surface are presented for some of the investigated cases. Using this element a few problems of curved laminated beams of bimodulus materials are solved for both solid and hollow circular cross-sections.

Monoblock cylinder internally pressurised under asymmetric end constraints Some aspects of design

The finite element method is used to analyse stresses and displacements in a monoblock cylinder open at one end only. The cylinder is internally pressurised. The analysis shows that the minimum pressure required to cause yield in the cylinder decreases rapidly with increasing cylinder height until the height is about the same as the outer radius of the cylinder, beyond which the decrease is marginal. Introduction of a fillet at the internal corner enhances the design pressure substantially while a fillet at the outer corner affects this pressure only marginally.

Low-density koala (Phascolarctos cinereus) populations in the mulgalands of south-west Queensland. II. Distribution and diet

This study used faecal pellets to investigate the broadscale distribution and diet of koalas in the mulgalands biogeographic region of south-west Queensland. Koala distribution was determined by conducting faecal pellet searches within a 30-cm radius of the base of eucalypts on 149 belt transects, located using a multi-scaled stratified sampling design. Cuticular analysis of pellets collected ffom 22 of these sites was conducted to identify the dietary composition of koalas within the region. Our data suggest that koala distribution is concentrated in the northern and more easterly regions of the study area, and appears to be strongly linked with annual rainfall. Over 50% of our koala records were obtained from non-riverine communities, indicating that koalas in the study area are not primarily restricted to riverine communities, as bas frequently been suggested. Cuticular analysis indicates that more than 90% of koala diet within the region consists of five eucalypt species. Our data highlights the importance of residual Tertiary landforms to koala conservation in the region.

An investigation of structural, magnetic and dielectric properties of R2NiMnO6 (R = rare earth, Y)

We have investigated the structure, magnetic and dielectric properties of the double perovskite oxides, R2NiMnO6 (R = Pr, Nd, Sm, Gd, Tb, Dy, Ho and Y). We could refine powder X-ray diffraction patterns of all the phases on the basis of monoclinic (P2(1)/n) double perovskite structure where Ni and Mn atoms are ordered at 2c and 2d sites, respectively. All the phases are ferromagnetic insulators exhibiting relatively low dielectric loss and dielectric constants in the range 15-25. The ferromagnetic ordering temperature of the R2NiMnO6 series seems to correlate better with the radius of R3+ atoms than with the average Ni-O-Mn angle (phi) in the double perovskite structure. These results are consistent with all samples having Mn4+ and Ni2+ With minimal antisite disorder.

An Exact Analysis of Unsteady Convective Diffusion in an Annular Pipe

An exact solution to the unsteady convective diffusion equation for the dispersion of a solute in a fully developed laminar flow in an annular pipe is obtained. Generalized dispersion model which is valid for all time after the injection of solute in the flow is used to evaluate the dispersion coefficients as functions of time. It is observed that the axial dispersion decreases with an increase in the radius of the inner cylinder.

Film cooling at hypersonic Mach numbers using forward facing array of micro-jets

Experimental investigations are carried out in the IISc hypersonic shock tunnel on film cooling effectiveness of a single jet (diameter 2 mm and 0.9 mm), and an array forward facing of micro-jets (diameter 300 mu m each) of same effective area (corresponding to the respective single jet). The single jet and the corresponding micro-jets are injected from the stagnation zone of a blunt cone model (58, apex angle and nose radius of 35 mm). Nitrogen and Helium are injected as coolant gases. Experiments are performed at freestream Mach number 5.9, at 0 degrees angle of attack, with a stagnation enthalpy of 1.84 MJ/kg, with and without injections. The ratios of the jet stagnation pressure to the freestream pitot pressure used in the present study are 1.2 and 1.45. Up to 50% reduction in surface heat transfer rate was observed with the array of micro-jets, compared to that of the respective single jet with nitrogen as the coolant, while the corresponding eduction was up to 37% for helium injection, with the schlieren flow visualizations showing no major change in the shock standoff distance, and thus no major changes in other aerodynamic aspects such as drag.

Surveillance protocols for management of invasive plants: modelling Chilean needle grass (Nassella neesiana) in Australia

Aim: To develop a surveillance support model that enables prediction of areas susceptible to invasion, comparative analysis of surveillance methods and intensity and assessment of eradication feasibility. To apply the model to identify surveillance protocols for generalized invasion scenarios and for evaluating surveillance and control for a context-specific plant invasion. Location: Australia. Methods: We integrate a spatially explicit simulation model, including plant demography and dispersal vectors, within a Geographical Information System. We use the model to identify effective surveillance protocols using simulations of generalized plant life-forms spreading via different dispersal mechanisms in real landscapes. We then parameterize the surveillance support model for Chilean needle grass [CNG; Nassella neesiana (Trin. & Rupr.) Barkworth], a highly invasive tussock grass, which is an eradication target in south-eastern Queensland, Australia. Results: General surveillance protocols that can guide rapid response surveillance were identified; suitable habitat that is susceptible to invasion through particular dispersal syndromes should be targeted for surveillance using an adaptive seek-and-destroy method. The search radius of the adaptive method should be based on maximum expected dispersal distances. Protocols were used to define a surveillance strategy for CNG, but simulations indicated that despite effective and targeted surveillance, eradication is implausible at current intensities. Main conclusions: Several important surveillance protocols emerged and simulations indicated that effectiveness can be increased if they are followed in rapid response surveillance. If sufficient data are available, the surveillance support model should be parameterized to target areas susceptible to invasion and determine whether surveillance is effective and eradication is feasible. We discovered that for CNG, regardless of a carefully designed surveillance strategy, eradication is implausible at current intensities of surveillance and control and these efforts should be doubled if they are to be successful. This is crucial information in the face of environmentally and economically damaging invasive species and large, expensive and potentially ineffective control programmes.