Kinetic and mechanistic study on the thermal reactivity of stabilized phosphorus ylides,part 3: [(Acetyl)(arylcarbamoyl)methylene]triphenylphosphoranes and [(alkoxycarbonyl)(arylcarbamoyl)methylene]triphenylphosphoranes and their thiocarbamoyl analogues

A series of five [(acetyl)(arylcarbabmoyl)methylene]triphenyl‐phosphoranes 1a–e and their thiocarbamoyl analogues 2a–e , [(alkoxycarbonyl)(arylcarbamoyl)methylene]triphenylphosphoranes 3a–e and their thiocarbamoyl analogues 4a–e were prepared and fully characterized. All ylides are found under conditions of flash vacuum pyrolysis to fragment giving arylisocyanate or isothiocyanate and acetyl ylides or alkoxy ylides which undergo thermal extrusion of Ph₃PO. A kinetic study shows that these reactions are unimolecular and are of first‐order nature with no significant substituent effect. The thiocarbamoyl ylides 2 react from 4.6 to 42 times faster than their carbamoyl ylides 1 , while the thiocarbamoyl ylides 4 react from 6.6 to 20.9 times faster than their carbamoyl ylides 3 . © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 39: 6–16, 2007     

Multi swarms for neighbor selection in peer-to-peer overlay networks

Peer-to-peer (P2P) topology has a significant influence on the performance, search efficiency and functionality, and scalability of the application. In this paper, we investigate a multi-swarm approach to the problem of neighbor selection (NS) in P2P networks. Particle swarm share some common characteristics with P2P in the dynamic socially environment. Each particle encodes the upper half of the peer-connection matrix through the undirected graph, which reduces the search space dimension. The portion of the adjustment to the velocity influenced by the individual’s cognition, the group cognition from multi-swarms, and the social cognition from the whole swarm, makes an important influence on the particles’ ergodic and synergetic performance. We also attempt to theoretically prove that the multi-swarm optimization algorithm converges with a probability of 1 towards the global optima. The performance of our approach is evaluated and compared with other two different algorithms. The results indicate that it usually required shorter time to obtain better results than the other considered methods, specially for large scale problems.     

A new 2-D model for operating point shift in large LWIR HgCdTeFPA's

Infrared focal plane arrays (IRFPAs) are rapidly increasing in size. It is shown here that for large FPAs a considerable shift in the operating point occurs, which, if not reduced, introduces unacceptably large nonuniformity in the array response. This shift results because of the variable voltage drop across the HgCdTe active layer, due to its finite distributed resistance. A new analytical two-dimensional (2-D) model to estimate the operating point shift of individual detectors of long wavelength infrared (LWIR) HgCdTe focal plane array (FPA) is presented. Avoiding this operating point shift requires an optimized grid pattern     

Synthesis,thermal reactivity,and kinetics of stabilized phosphorus ylides,part 2: [(Arylcarbamoyl)(cyano)methylene]triphenylphosphoranes and their thiocarbamoyl analogues

A series of five cyano(arylcarbamoyl) phosphorus ylides 2 and five cyano(arylthiocarbamoyl) phosphorus ylides 3 are prepared and fully characterized. Pyrolytic reaction products of a representative example of each type obtained by flash vacuum pyrolysis technique show that they undergo thermal extrusion of Ph₃PO or Ph₃PS. Kinetic study of the gas‐phase pyrolysis of each ylide by static method shows that these reactions are unimolecular and first order with no significant substituent effect, but the thiocarbamoyl ylides 3 react 40–65 times more rapidly than their carbamoyl analogues 2 . © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 496–502, 2006     

Role of diet and trace elements in lithogenesis of renal calculi

Twenty eight stones were characterized for chemical composition and structure. The concentrations of trace elements were determined using INAA while EDXRF was used for determining the calcium contents of the stones. Twenty stones were found to be mainly composed of calcium, six were mixed type and the remaining two were of uric acid type. The concentrations of trace elements namely Zn, Sr, Fe and Cr were lower in uric acid stones as compared to calcium based stones. Diet analysis of 310 patients who were treated for renal stones showed a diet rich in calcium and oxalate and decreased water consumption.

     

Benchmark studies on the building blocks of DNA. 1. Superiority of coupled cluster methods in describing the excited states of nucleobases in the Franck-Condon region

Equation of motion excitation energy coupled-cluster (EOMEE-CC) methods including perturbative triple excitations have been used to set benchmark results for the excitation energy and oscillator strength of the building units of DNA, i.e., cytosine, guanine, adenine and thymine. In all cases the lowest twelve transitions have been considered including valence and Rydberg ones. Triple-ζ basis sets with diffuse functions have been used and the results are compared to CC2, CASPT2, TDDFT, and DFT/MRCI results from the literature. The results clearly show that it is only the EOMEE-CCSD(T) that is capable of providing accuracy of about 0.1 eV. EOMEE-CCSD systematically overshoots the energy of all types of transitions by 0.1-0.3 eV, whereas CC2 is surprisingly accurate for ππ* transitions but fails (often badly) for nπ* and Rydberg transitions. DFT and CASPT2 seem to give reliable results for the lowest transition, but the error increases fast with the excitation level. The differences in the excitation energies often change the energy ordering of the states, which should even influence the conclusions of excited state dynamics obtained with these approximate methods. The results call for further benchmark calculations on larger building blocks of DNA (nucleosides, basis pairs) at the CCSD(T) level.     

Large sample neutron activation analysis of dross for gold and silver

Large sample neutron activation analysis of dross from India Government Mint, Mumbai was carried out for quantification of gold (Au) and silver (Ag) using graphite reflector position of Advanced Heavy Water Reactor critical facility at Bhabha Atomic Research Centre, Mumbai. The k ₀-based internal monostandard NAA was used to calculate concentration ratios of Au and Ag with respect to sodium (Na), which was used as an internal monostandard. The concentration ratio values of Au to Na of varying mass of dross showed that mass ≥2 g was the representative sample size for analysis. Concentrations of gold and silver were found to be in the range of 200–400 and 1200–1700 mg kg^?1, respectively in three different samples.     

An adaptive scanning scheme for effective whole field stress separation in digital photoelasticity

In photoelasticity, the method of obtaining the individual values of principal stresses/normal stresses separately is referred to as stress separation. Shear difference method is one of the widely used techniques for stress separation in digital photoelasticity. Normally a simple raster scanning approach is used in shear difference method in which stress separation is carried out for all the lines within the model domain by either row-wise horizontally or column-wise vertically starting from the boundary pixels. This requires the presence of a free boundary to start the integration scheme for every row of interest, which is not always possible in most of the practical problems. In order to overcome this, in this paper, an adaptive scanning scheme is proposed so that stress separation can be carried out even if there is only one free boundary pixel available in the model. The new scanning scheme is validated using the theoretically generated data for the problem of a ring subjected to internal pressure. Later, the applicability of this scheme is demonstrated by using two other example problems.     

A live fringe technique for stress measurements in reflecting thin films, using holography

A simple technique is given for measuring stresses in reflecting thin films, using real-time holography. The technique gives clear real fringes with good visibility which can be easily monitored and photographed. No substrate profile measurement is needed. Thermal stress of 0.49 × 10⁹ dynes cm^-2 is observed for a 200.0 nm thick Ag film in the temperature range of 30 to 55°C. This is in good agreement with reported values.