Enantiodiscrimination and extraction of short and long range homo- and hetero-nuclear residual dipolar couplings by a spin selective correlation experiment

A two dimensional correlation experiment for the measurement of short and long range homo- and hetero- nuclear residual dipolar couplings (RDCs) from the broad and featureless proton NMR spectra including C-13 satellites is proposed. The method employs a single natural abundant C-13 spin as a spy nucleus to probe all the coupled protons and permits the determination of RDCs of negligible strengths. The technique has been demonstrated for the study of organic chiral molecules aligned in chiral liquid crystal, where additional challenge is to unravel the overlapped spectrum of enantiomers. The significant advantage of the method is demonstrated in better chiral discrimination using homonuclear RDCs as additional parameters. (C) 2010 Elsevier B.V. All rights reserved.

Estimation of soil hydraulic properties and their uncertainty: comparison between laboratory and field experiment

Often the soil hydraulic parameters are obtained by the inversion of measured data (e.g. soil moisture, pressure head, and cumulative infiltration, etc.). However, the inverse problem in unsaturated zone is ill-posed due to various reasons, and hence the parameters become non-unique. The presence of multiple soil layers brings the additional complexities in the inverse modelling. The generalized likelihood uncertainty estimate (GLUE) is a useful approach to estimate the parameters and their uncertainty when dealing with soil moisture dynamics which is a highly non-linear problem. Because the estimated parameters depend on the modelling scale, inverse modelling carried out on laboratory data and field data may provide independent estimates. The objective of this paper is to compare the parameters and their uncertainty estimated through experiments in the laboratory and in the field and to assess which of the soil hydraulic parameters are independent of the experiment. The first two layers in the field site are characterized by Loamy sand and Loamy. The mean soil moisture and pressure head at three depths are measured with an interval of half hour for a period of 1 week using the evaporation method for the laboratory experiment, whereas soil moisture at three different depths (60, 110, and 200 cm) is measured with an interval of 1 h for 2 years for the field experiment. A one-dimensional soil moisture model on the basis of the finite difference method was used. The calibration and validation are approximately for 1 year each. The model performance was found to be good with root mean square error (RMSE) varying from 2 to 4 cm(3) cm(-3). It is found from the two experiments that mean and uncertainty in the saturated soil moisture (theta(s)) and shape parameter (n) of van Genuchten equations are similar for both the soil types. Copyright (C) 2010 John Wiley & Sons, Ltd.

Sensitivity of the simulated precipitation to changes in convective relaxation time scale

The paper describes the sensitivity of the simulated precipitation to changes in convective relaxation time scale (TAU) of Zhang and McFarlane (ZM) cumulus parameterization, in NCAR-Community Atmosphere Model version 3 (CAM3). In the default configuration of the model, the prescribed value of TAU, a characteristic time scale with which convective available potential energy (CAPE) is removed at an exponential rate by convection, is assumed to be 1 h. However, some recent observational findings suggest that, it is larger by around one order of magnitude. In order to explore the sensitivity of the model simulation to TAU, two model frameworks have been used, namely, aqua-planet and actual-planet configurations. Numerical integrations have been carried out by using different values of TAU, and its effect on simulated precipitation has been analyzed. The aqua-planet simulations reveal that when TAU increases, rate of deep convective precipitation (DCP) decreases and this leads to an accumulation of convective instability in the atmosphere. Consequently, the moisture content in the lower-and mid-troposphere increases. On the other hand, the shallow convective precipitation (SCP) and large-scale precipitation (LSP) intensify, predominantly the SCP, and thus capping the accumulation of convective instability in the atmosphere. The total precipitation (TP) remains approximately constant, but the proportion of the three components changes significantly, which in turn alters the vertical distribution of total precipitation production. The vertical structure of moist heating changes from a vertically extended profile to a bottom heavy profile, with the increase of TAU. Altitude of the maximum vertical velocity shifts from upper troposphere to lower troposphere. Similar response was seen in the actual-planet simulations. With an increase in TAU from 1 h to 8 h, there was a significant improvement in the simulation of the seasonal mean precipitation. The fraction of deep convective precipitation was in much better agreement with satellite observations.

Application of a modified z-cosy experiment for the analysis of spectra of oriented molecules - the spectrum of cis,cis-mucanonitrile

NMR spectra of cis,cis-mucanonitrile oriented in a liquid crystal have been analysed using the connectivity information obtained from a modified Z-COSY experiment which provided crucial clues for the starting parameters for the iterative analysis. The proton spectra with and without C-13 satellites and the C-13 spectra have thus been interpreted. The indirect spin-spin couplings required for the analyses have been obtained from the corresponding isotropic spectra. The H-1-H-1 and C-13-H-1 dipolar couplings so obtained have been utilized to determine the relative internuclear distances. The results indicate that the molecule is planar. (C) 1994 Academic Press, Inc.

Construction of energy-level diagram of oriented benzene using connectivity information obtained by modified z-cosy experiment

Experiments involving selective perturbation of a transition yield information about the directly connected transitions, which in turn yield information for deriving the parameters of the spin Hamiltonian of oriented molecules. Problems involved with selective perturbation are removed by the use of a two-dimensional experiment, namely, the modified Z-COSY-experiment, The use of this experiment is demonstrated for obtaining the connectivity information and for determining the parameters of the spin Hamiltonian of oriented benzene, a strongly coupled six-spin system

An Efficient Simulated Annealing With a Valid Solution Mechanism For TDMA Brodcast Scheduling problem

This paper presents an efficient Simulated Annealing with valid solution mechanism for finding an optimum conflict-free transmission schedule for a broadcast radio network. This is known as a Broadcast Scheduling Problem (BSP) and shown as an NP-complete problem, in earlier studies. Because of this NP-complete nature, earlier studies used genetic algorithms, mean field annealing, neural networks, factor graph and sum product algorithm, and sequential vertex coloring algorithm to obtain the solution. In our study, a valid solution mechanism is included in simulated annealing. Because of this inclusion, we are able to achieve better results even for networks with 100 nodes and 300 links. The results obtained using our methodology is compared with all the other earlier solution methods.

Gas-liquid nucleation at large metastability: unusual features and a new formalism

Nucleation at large metastability is still largely an unsolved problem, even though it is a problem of tremendous current interest, with wide-ranging practical value, from atmospheric research to materials science. It is now well accepted that the classical nucleation theory (CNT) fails to provide a qualitative picture and gives incorrect quantitative values for such quantities as activation-free energy barrier and supersaturation dependence of nucleation rate, especially at large metastability. In this paper, we present an alternative formalism to treat nucleation at large supersaturation by introducing an extended set of order parameters in terms of the kth largest liquid-like clusters, where k = 1 is the largest cluster in the system, k = 2 is the second largest cluster and so on. At low supersaturation, the size of the largest liquid-like cluster acts as a suitable order parameter. At large supersaturation, the free energy barrier for the largest liquid-like cluster disappears. We identify this supersaturation as the one at the onset of kinetic spinodal. The kinetic spinodal is system-size-dependent. Beyond kinetic spinodal many clusters grow simultaneously and competitively and hence the nucleation and growth become collective. In order to describe collective growth, we need to consider the full set of order parameters. We derive an analytic expression for the free energy of formation of the kth largest cluster. The expression predicts that, at large metastability (beyond kinetic spinodal), the barrier of growth for several largest liquid-like clusters disappears, and all these clusters grow simultaneously. The approach to the critical size occurs by barrierless diffusion in the cluster size space. The expression for the rate of barrier crossing predicts weaker supersaturation dependence than what is predicted by CNT at large metastability. Such a crossover behavior has indeed been observed in recent experiments (but eluded an explanation till now). In order to understand the large numerical discrepancy between simulation predictions and experimental results, we carried out a study of the dependence on the range of intermolecular interactions of both the surface tension of an equilibrium planar gas-liquid interface and the free energy barrier of nucleation. Both are found to depend significantly on the range of interaction for the Lennard-Jones potential, both in two and three dimensions. The value of surface tension and also the free energy difference between the gas and the liquid phase increase significantly and converge only when the range of interaction is extended beyond 6-7 molecular diameters. We find, with the full range of interaction potential, that the surface tension shows only a weak dependence on supersaturation, so the reason for the breakdown of CNT (with simulated values of surface tension and free energy gap) cannot be attributed to the supersaturation dependence of surface tension. This remains an unsettled issue at present because of the use of the value of surface tension obtained at coexistence.

Genesis of the monsoon trough boundary layer experiment (MONTBLEX)

This paper sets out the motivation for carrying out an observational experiment on the atmospheric boundary layer along the monsoon trough, in the light of earlier studies of the atmospheric boundary layer in India and elsewhere, and the significant role that the trough has been shown to play as a key semi-permanent feature of the southwest monsoon. The scientific objectives of the experiment are set out, and its planning and execution are touched upon. Some of the gains resulting from the experiment are mentioned, and lessons for the future about the conduct of such programmes are drawn.

Modelling plane mixing layers using vortex points and sheets

We present here a critical assessment of two vortex approaches (both two-dimensional) to the modelling of turbulent mixing layers. In the first approach the flow is represented by point vortices, and in the second it is simulated as the evolution of a continuous vortex sheet composed of short linear elements or ''panels''. The comparison is based on fresh simulations using approximately the same number of elements in either model, paying due attention in both to the boundary conditions far downstream as well as those on the splitter plate from which the mixing layer issues. The comparisons show that, while both models satisfy the well-known invariants of vortex dynamics approximately to the same accuracy, the vortex panel model, although ultimately not convergent, leads to smoother roll-up and values of stresses and moments that are in closer agreement with the experiment, and has a higher computational efficiency for a given degree of convergence on moments. The point vortex model, while faster for a given number of elements, produces an unsatisfactory roll-up which (for the number of elements used) is rendered worse by the incorporation of the Van der Vooren correction for sheet curvature.

Spin-Selective Correlation Experiment for Measurement of Long-Range J Couplings and for Assignment of (R/S) Enantiomers from the Residual Dipolar Couplings and DFT

We report the C-HETSERF experiment for determination of long- and short-range homo- and heteronuclear scalar couplings ((n)J(HH) and (n)J(XH), n >= 1) of organic molecules with a low sensitivity dilute heteronucleus in natural abundance. The method finds significant advantage in measurement of relative signs of long-range heteronuclear total couplings in chiral organic liquid crystal. The advantage of the method is demonstrated for the measurement of residual dipolar couplings (RDCs) in enantiomers oriented in the chiral liquid crystal with a focus to unambiguously assign R/S designation in a 2D spectrum. The alignment tensor calculated from the experimental RDCs and with the computed structures of enantiomers obtained by DFT calculations provides the size of the back-calculated RDCs. Smaller root-mean-square deviations (rmsd) between experimental and calculated RDCs indicate better agreement with the input structure and its correct designation of the stereogenic center.

Mutagenic significance of proton acidities in methylated guanine and thymine bases and deoxynucleosides: A theoretical study

Proton changes have been advanced as being the key molecular basis for the mutagenecity of alkylated DNA bases and nucleosides, leading to questions as to which protons are involved and whether the protic changes are tautomeric shifts or abstractions. This semiempirical molecular orbital study seeks to clarify the issue by examining the various possibilities open for these protic changes in a number of methylated guanines and thymines and their deoxynucleosides. Proton shifts leading to tautomer formation are not predicted as being thermodynamically favourable in most cases. The most feasible proton abstractions are predicted to involve the Watson-Crick protons in all cases, which corroborates Watson-Crick proton loss as providing the key molecular basis for the induction of point mutations. The calculated proton acidities correlate well with experimental data. The gas-phase deprotonation enthalpies for a number of alkylated nucleosides are found to correlate linearly with the solvent-phase pK(a) values. The theoretically calculated enthalpies in a simulated aqueous solvent phase of the deprotonation reactions of various nucleic acid bases are also found to have good linear correlations with experimental pK(a) values. The consensus of these calculations is that O-6-alkyldeoxyguanosines, and O-2- and O-4-alkyldeoxythymidines would be mutagenic while N-7-alkyldeoxyguanosines would not be mutagenic (as experiment indicates). The untested N-3-methyldeoxyguanosine is predicted to be mutagenic. (C) 1997 Elsevier Science B.V.