Syntheses, spectroscopy, structures, and conformations of .lambda.3-cyclotriphosphazanes: role of negative hyperconjugation

The reactions of As-chlorocyclotriphosphazane [EtNPCl], with phenols or trifluoroethanol yield the respective aryloxy- or trifluoroethoxy-containingX 3-cyclotriphosphazanes [EtNP(OR)]3 (R = C6H4Br-4 (2),C 6H5 (3C,6 H3-Mez-3,5 (4), C6H3Mez-2,6 (5), CH2CF3 (6)) as their cis-transisomericmixtures. The products have beencharacterized by IRand NMRspectroscopy. Thecrystalstructuresofboth thecis (2a) and trans(2b) isomer_softhep-bromophenoxy derivative have been determined by X-ray diffraction. Crystal data for 2a: triclinic, P1, a = 9.872(4) A, b = 13.438(6) A, c = 13.548(8) A, CY = 117.02(5)', 0 = 96.00(6)', y = 105.38(4)O, Z = 2, final R = 0.080. Crystal data for 2b: monoclinic, P21/n, a = 12.721(6) A, b = 13.468(7) A, c = 17.882(5) A, /3 = 101.62(3)O, Z = 4, final R = 0.066. The cis isomer exhibits a chair-triaxial conformation and the trans isomer a boat-triaxial conformation. Conformational preferences of X3-cyclotriphosphazanes have been probed by both MNDO and ab initio calculations on model systems [HNPXIp (X = H, F). In addition to vicinal lone pair repulsions, negative hyperconjugative interactions involving the nitrogen lone pairs and adjacent P-X Q* orbitals are found to be important (especially when X is an electronegative substituent) in determining the conformational preferences of X3-cyclotriphosphazanes. The calculations also show that the axial - equatorial conversion at phosphorus has a large activation barrier in these systems

Numerical Electromagnetic Analysis of Current and Voltage Distribution along Down Conductors and Towers Hit by Direct Lightning

In order to answer the practically important question of whether the down conductors of lightning protection systems to tall towers and buildings can be electrically isolated from the structure itself, this work is conducted. As a first step in this regard, it is presumed that the down conductor placed on metallic tower will be a pessimistic representation of the actual problem. This opinion was based on the fact that the proximity of heavy metallic structure will have a large damping effect. The post-stroke current distributions along the down conductors and towers, which can be quite different from that in the lightning channel, govern the post-stroke near field and the resulting gradient in the soil. Also, for a reliable estimation of the actual stroke current from the measured down conductor currents, it is essential to know the current distribution characteristics along the down conductors. In view of these, the present work attempts to deduce the post-stroke current and voltage distribution along typical down conductors and towers. A solution of the governing field equations on an electromagnetic model of the system is sought for the investigation. Simulation results providing the spatio-temporal distribution of the post-stroke current and voltage has provided very interesting results. It is concluded that it is almost impossible to achieve electrical isolation between the structure and the down conductor. Furthermore, there will be significant induction into the steel matrix of the supporting structure.

Generalized State Parameter for Partly Saturated Soils

Studies on compressibility and shear strength aspects are the concern of many investigators concerned with partly saturated soils. In soil engineering connected with partly saturated soils, there are no approaches connecting soil states and stress conditions. The present investigation is essentially a step in this direction. A generalized state parameter, identified with regard to material states is shown to be related to the compressibility and shear strength. The involved parameters are simple and normally determined in routine investigations. The advantage of this approach is that changes in soil states due to external stress conditions and the associated changes in strength can be examined particularly when different types of soils are involved.

Geographical Distribution Patterns of Amphibians in the Western Ghats, India

The Western Ghats of India are very rich in amphibian species with 117 species of frogs, toads and caecilians. Eighty-nine species are endemic to this biogeographical region. Analysis of ranges and patterns of geographical distribution of amphibians on the Western Ghats suggest that the southern half of the Western Ghats and the low-medium elevation hills are more diverse in species than the northern half and higher hills. This is attributed to the more widespread rainfall and the less variable climatic conditions in the south. About half the species are apparently localized. Of those species with wider ranges, a majority show patchy distribution. Species preferring the moist evergreen forests as habitats tend to have patchy distributions. This appears to be a result of habitat destruction and fragmentation. The overall patterns of species richness and local endemism are rather different from those of the angiosperms and birds. In birds and angiosperms, a significant proportion of endemics are found on the higher hills. On the contrary, endemic amphibian species are found in the lower altitudinal range of 0-1000 m, with a majority between 800 and 1000 m.

Persistence Problem in Two-Dimensional Fluid Turbulence

We present a natural framework for studying the persistence problem in two-dimensional fluid turbulence by using the Okubo-Weiss parameter Lambda to distinguish between vortical and extensional regions. We then use a direct numerical simulation of the two-dimensional, incompressible Navier-Stokes equation with Ekman friction to study probability distribution functions (PDFs) of the persistence times of vortical and extensional regions by employing both Eulerian and Lagrangian measurements. We find that, in the Eulerian case, the persistence-time PDFs have exponential tails; by contrast, this PDF for Lagrangian particles, in vortical regions, has a power-law tail with an exponent theta = 2.9 +/- 0.2.

An unusual distribution of glucose-6-phosphate dehydrogenase deficiency of south Indian newborn population.

Glucose-6-phosphate dehydrogenase (G6PD) deficiency is seen at a higher frequency in many national and ethnic groups in areas of current or former malaria endemicity. A screening programme undertaken to evaluate the gene frequencies for this deficiency in the highly inbred South Indian population of Karnataka revealed that of the 5140 neonates screened, 7.8% were G6PD deficient with no correlation between the reported level of inbreeding and enzyme deficiency. An interesting finding was the equal number of male (198) and female (207) individuals, with G6PD activity of less than 3 IU. The possible implications of this finding with regard to the expression of G6PD gene is discussed.

Distribution of ionic charge carriers and migration barriers in binary alkali silicate glasses

Likely spatial distributions of network-modifying (and mobile) cations in (oxide) glasses are discussed here. At very low modifier concentrations, the ions form dipoles with non-bridging oxygen centres while, at higher levels of modification, the cations tend to order as a result of Coulombic interactions. Activation energies for cation migration are calculated, assuming that the ions occupy (face-sharing) octahedral sites. It is found that conductivity activation energy decreases markedly with increasing modifier content, in agreement with experiment.

Xenon in sodium Y zeolite. 2. Arrhenius relation, mechanism, and barrier height distribution for cage-to-cage diffusion

Various geometrical and energetic distribution functions and other properties connected with the cage-to-cage diffusion of xenon in sodium Y zeolite have been obtained from long molecular dynamics calculations. Analysis of diffusion pathways reveals two interesting mechanisms-surface-mediated and centralized modes for cage-to-cage diffusion. The surface-mediated mode of diffusion exhibits a small positive barrier, while the centralized diffusion exhibits a negative barrier for the sorbate to diffuse across the 12-ring window. In both modes, however, the sorbate has to be activated from the adsorption site to enable it to gain mobility. The centralized diffusion additionally requires the sorbate to be free of the influence of the surface of the cage as well. The overall rate for cage-to-cage diffusion shows an Arrhenius temperature dependence with E(a) = 3 kJ/mol. It is found that the decay in the dynamical correction factor occurs on a time scale comparable to the cage residence time. The distributions of barrier heights have been calculated. Functions reflecting the distribution of the sorbate-zeolite interaction at the window and the variations of the distance between the sorbate and the centers of the parent and daughter cages are presented.

Measurement of complex optical flow with use of an augmented generalized gradient scheme

We present a method for measuring the local velocities and first-order variations in velocities in a timevarying image. The scheme is an extension of the generalized gradient model that encompasses the local variation of velocity within a local patch of the image. Motion within a patch is analyzed in parallel by 42 different spatiotemporal filters derived from 6 linearly independent spatiotemporal kernels. No constraints are imposed on the image structure, and there is no need for smoothness constraints on the velocity field. The aperture problem does not arise so long as there is some two-dimensional structure in the patch being analyzed. Among the advantages of the scheme is that there is no requirement to calculate second or higher derivatives of the image function. This makes the scheme robust in the presence of noise. The spatiotemporal kernels are of simple form, involving Gaussian functions, and are biologically plausible receptive fields. The validity of the scheme is demonstrated by application to both synthetic and real video images sequences and by direct comparison with another recently published scheme Biol. Cybern. 63, 185 (1990)] for the measurement of complex optical flow.

Measurement of complex optical flow with use of an augmented generalized gradient scheme

We present a method for measuring the local velocities and first-order variations in velocities in a time-varying image. The scheme is an extension of the generalized gradient model that encompasses the local variation of velocity within a local patch of the image. Motion within a patch is analyzed in parallel by 42 different spatiotemporal filters derived from 6 linearly independent spatiotemporal kernels. No constraints are imposed on the image structure, and there is no need for smoothness constraints on the velocity field. The aperture problem does not arise so long as there is some two-dimensional structure in the patch being analyzed. Among the advantages of the scheme is that there is no requirement to calculate second or higher derivatives of the image function. This makes the scheme robust in the presence of noise. The spatiotemporal kernels are of simple form, involving Gaussian functions, and are biologically plausible receptive fields. The validity of the scheme is demonstrated by application to both synthetic and real video images sequences and by direct comparison with another recently published scheme [Biol. Cybern. 63, 185 (1990)] for the measurement of complex optical flow.

Parameter estimation in water-distribution systems by least squares

The weighted-least-squares method using sensitivity-analysis technique is proposed for the estimation of parameters in water-distribution systems. The parameters considered are the Hazen-Williams coefficients for the pipes. The objective function used is the sum of the weighted squares of the differences between the computed and the observed values of the variables. The weighted-least-squares method can elegantly handle multiple loading conditions with mixed types of measurements such as heads and consumptions, different sets and number of measurements for each loading condition, and modifications in the network configuration due to inclusion or exclusion of some pipes affected by valve operations in each loading condition. Uncertainty in parameter estimates can also be obtained. The method is applied for the estimation of parameters in a metropolitan urban water-distribution system in India.

Solvation dynamics, energy distribution and trapping of a light solute ion

In the theoretical treatments of the dynamics of solvation of a newly created ion in a dipolar solvent, the self-motion of the solute is usually ignored. Recently, it has been shown that for a light ion the translational motion of the ion can significantly enhance its own rate of solvation. Therefore, solvation itself may not be the rate determining step in the equilibration. Instead, the rate determining step is the search of the low energy configuration which serves to localize the light ion. In this article a microscopic calculation of the probability distribution of the interaction energy of the nascent charge with the dipolar solvent molecules is presented in order to address this problem of solute trapping. It is found that to a good approximation, this distribution is Gaussian and the second moment of this distribution is exactly equal to the half of its own solvation energy. It is shown that this is in excellent agreement with the simulation results that are available for the model Brownian dipolar lattice and for liquid acetonitrile. If the distortion of the solvent by the ion is negligible then the same relation gives the energy distribution for the solvated ion, with the average centered at the final equilibrium solvation energy. These results are expected to be useful in understanding various chemical processes in dipolar liquids. Another interesting outcome of the present study is a simple dynamic argument that supports Onsager's ''inverse snow-ball'' conjecture of solvation of a light ion. A simple derivation of the semi-phenomenological relation between the solvation time correlation function and the single particle orientation, reported recently by Maroncelli et al. (J. Phys. Chem. 97 (1993) 13), is also presented.

Reactions of palladium chloride with amino spirocyclic cyclotriphosphazenes: Isolation and Crystal Structures of Novel Mono- and Bimetallic Complexes Formed by the Hydrolysis of a .lambda.5-Diazaphospholane Ring

The reaction of the amino spirocyclic cyclotriphosphazene N3P3(NMe2)4(NHCH2CH2CH2NH) (2) with palladium chloride gives the stable chelate complex [PdCl2.2] (4). An X-ray crystallographic study reveals that one of the nitrogen atoms of the diaminoalkane moiety and an adjacent phosphazene ring nitrogen atom are bonded to the metal. An analogous reaction with the phosphazene N3P3(NMe2)4(NHCH2CH2NH) (1) gives initially a similar complex which undergoes facile hydrolysis to give the novel monometallic and bimetallic complexes [PdCl2.HN3P3(O)(NMe2)4(NHCH2CH2NH2)] (5) and [PdCl{N3P3(NMe2)4(NCH2CH2NH2)}]2(O) (6), which have been structurally characterized; in the former, an (oxophosphazadienyl)ethylenediamine is chelated to the metal whereas, in the latter, an oxobridged bis(cyclotriphosphazene) acts as a hexadentate nitrogen donor ligand in its dianionic form. Crystal data for 4 : a = 14.137(1) angstrom, b = 8.3332(5) angstrom, c = 19.205(2) angstrom, beta = 96.108(7)degrees, P2(1)/c, Z = 4, R = 0.027 with 3090 reflections (F > 5sigma(F)). Crystal data for 5 : a = 8.368(2) angstrom, b = 16.841(4) A, c = 16.092(5) angstrom, beta = 98.31(2)degrees, P2(1)/n, Z = 4, R = 0.049 with 3519 reflections (F > 5sigma(F)). Crystal data for 6 : a = 22.455(6) angstrom, b = 14.882(3) angstrom, c = 13.026(5) angstrom, 6 = 98.55(2)degrees, C2/c, Z = 4, R = 0.038 with 3023 reflections (F > 5sigma(F)).

Capturability of realistic generalized true proportional navigation

The capturability of a realistic generalized true proportional navigation (RGTPN) guidance law, against a nonmaneuvering target, is analyzed. The RGTPN law is obtained by relaxing the somewhat unrealistic assumption of constant closing velocity, made in all earlier studies on generalized true proportional navigation (GTPN), and incorporating the actual time-varying value in the guidance law. Closed-form solutions for the complete capture region of RGTPN is obtained in terms of both zero and acceptable non-zero miss distances. It is shown that the capture region of RGTPN in the initial relative velocity space is significantly smaller than that of GTPN, for reasonable values of navigation constant (N) and angular direction (eta) of the missile commanded latax. However, for certain values of N and eta, capturability of RGTPN is found to be better. It is also shown that if in one of the versions of GTPN, which uses constant values of both the closing velocity and the line-of-sight (LOS) angular velocity in the guidance law, the corresponding realistic time-varying quantities are used, the capture region actually expands to cover the whole of the initial relative velocity space. A number of examples are given to compare the capture performance of RGTPN with other versions of the GTPN guidance laws.

Characterization of the DNA-binding domain of beta protein, a component of phage lambda Red-pathway by UV catalyzed cross-linking

beta protein, a key component of Red-pathway of phage lambda is necessary for its growth and general genetic recombination in recombination-deficient mutants of Escherichia coli. To facilitate studies on structure-function relationships, we overexpressed beta protein and purified it to homogeneity. A chemical cross-linking reagent, glutaraldehyde, was used to stabilize the physical association of beta protein in solution. A 67-kDa band, corresponding to homodimer, was identified after separation by SDS-polyacrylamide gel electrophoresis. Stoichiometric measurements indicated a site-size of 1 monomer of beta protein/5 nucleotide residues. Electrophoretic gel mobility shift assays suggested that beta protein formed stable nucleoprotein complexes with 36-mer, but not with 27- or 17-mer DNA. Interestingly, the interaction of beta protein with DNA and the stability of nucleoprotein complexes was dependent on the presence of MgCl2, and the binding was abolished by 250 mM NaCl. The K-d of beta protein binding to 36-mer DNA was on the order of 1.8 x 10(-6) M. Photochemical cross-linking of native beta protein or its fragments, generated by chymotrypsin, to 36-mer DNA was performed to identify its DNA-binding domain. Characterization of the cross-linked peptide disclosed that amino acids required for DNA-binding specificity resided within a 20-kDa peptide at the N-terminal end. These findings provide a basis for further understanding oi the structure and function of beta protein.