NQR study of complexes between p-dichlorobenzene and some aromatic π acceptors

The charge-transfer complexes of p-dichlorobenzene (PDB) with some aromatic π acceptors such as m-nitrobenzaldehyde (MNB), picric acid (PA), p-nitrobenzoic acid (PNB), and m-dinitrobenzene (MDNB) were prepared by slowly adding the acceptor to the molten donor and then cooling the mass to 15°C. The NQR frequencies of these complexes were measured at room temperature. Contrary to the theoretical prediction, the NQR shift is positive, indicating that the NQR shift in donor-acceptor complexes is indirectly related to the charge-transfer interaction. Bond properties are discussed in terms of frequency shift.

Comparative study on damage identification from lso-Eigen-Value-Change contours and smeared damage model

The paper proposes two methodologies for damage identification from measured natural frequencies of a contiguously damaged reinforced concrete beam, idealised with distributed damage model. The first method identifies damage from Iso-Eigen-Value-Change contours, plotted between pairs of different frequencies. The performance of the method is checked for a wide variation of damage positions and extents. The method is also extended to a discrete structure in the form of a five-storied shear building and the simplicity of the method is demonstrated. The second method is through smeared damage model, where the damage is assumed constant for different segments of the beam and the lengths and centres of these segments are the known inputs. First-order perturbation method is used to derive the relevant expressions. Both these methods are based on distributed damage models and have been checked with experimental program on simply supported reinforced concrete beams, subjected to different stages of symmetric and un-symmetric damages. The results of the experiments are encouraging and show that both the methods can be adopted together in a damage identification scenario.

Electrical and Dielectric Behaviour at the Critical Point of Binary Liquids: Acetonitrile + Cyclohexane

The electrical capacitance and resistance of the binary liquid mixture cyclohexane + acetonitrile are measured in the one phase and two phase regions at spot frequencies between 5 kHz and 100 kHz. This sample has a very low gravity affected (∼0.6 mK) region. In one phase region the capacitance data show a sharp, ∼0.7% increase above background within 0.5 degrees of Tc whereas the resistance has a smooth increase of ∼1.5% above background in a (T−Tc) range of 4 degrees. Two phase values of capacitance and resistance from the coexisting phases are used to determine the critical parameters Tc (critical temperature), Rc (resistance at Tc) and Cc (capacitance at Tc). A precise knowledge of these parameters reduces the uncertainty on the critical exponent 0 for C and R. The one phase capacitance data fit to an (1 - α) exponent in a limited temperature range of 0.2 degrees. Resistance data strongly support an (1 - α) exponent over the entire 5 degree range.

Constraining uncertainty in regional hydrologic impacts of climate change: Nonstationarity in downscaling

Regional impacts of climate change remain subject to large uncertainties accumulating from various sources, including those due to choice of general circulation models (GCMs), scenarios, and downscaling methods. Objective constraints to reduce the uncertainty in regional predictions have proven elusive. In most studies to date the nature of the downscaling relationship (DSR) used for such regional predictions has been assumed to remain unchanged in a future climate. However,studies have shown that climate change may manifest in terms of changes in frequencies of occurrence of the leading modes of variability, and hence, stationarity of DSRs is not really a valid assumption in regional climate impact assessment. This work presents an uncertainty modeling framework where, in addition to GCM and scenario uncertainty, uncertainty in the nature of the DSR is explored by linking downscaling with changes in frequencies of such modes of natural variability. Future projections of the regional hydrologic variable obtained by training a conditional random field (CRF) model on each natural cluster are combined using the weighted Dempster-Shafer (D-S) theory of evidence combination. Each projection is weighted with the future projected frequency of occurrence of that cluster (''cluster linking'') and scaled by the GCM performance with respect to the associated cluster for the present period (''frequency scaling''). The D-S theory was chosen for its ability to express beliefs in some hypotheses, describe uncertainty and ignorance in the system, and give a quantitative measurement of belief and plausibility in results. The methodology is tested for predicting monsoon streamflow of the Mahanadi River at Hirakud Reservoir in Orissa, India. The results show an increasing probability of extreme, severe, and moderate droughts due to limate change. Significantly improved agreement between GCM predictions owing to cluster linking and frequency scaling is seen, suggesting that by linking regional impacts to natural regime frequencies, uncertainty in regional predictions can be realistically quantified. Additionally, by using a measure of GCM performance in simulating natural regimes, this uncertainty can be effectively constrained.

Chlorine-35 nuclear quadrupole resonance study of molecular torsional motion in some chloropyridine-N-oxides and chloroquinoline-N-oxides

Chlorine has been substituted at the 2- and 4-positions in the pyridine and quinoline rings of the corresponding N-oxides and 35Cl n.q.r. spectra have been studied in the temperature range 77–300 K. The change in the n.q.r. frequencies in N-oxides as compared to their parent compounds are interpreted in terms of the conjugative effect and the inductive effect of the N+—O– group. The negative temperature coefficients of the resonance frequencies in chloropyridine-N-oxides have been analysed using the Bayer, Kushida and Brown equations. The calculated torsional frequencies, which are in the range 52–78 cm–1, are found to be only slightly temperature dependent.

Filter design using radial basis function neural network and genetic algorithm for improved operational health monitoring

The problem of denoising damage indicator signals for improved operational health monitoring of systems is addressed by applying soft computing methods to design filters. Since measured data in operational settings is contaminated with noise and outliers, pattern recognition algorithms for fault detection and isolation can give false alarms. A direct approach to improving the fault detection and isolation is to remove noise and outliers from time series of measured data or damage indicators before performing fault detection and isolation. Many popular signal-processing approaches do not work well with damage indicator signals, which can contain sudden changes due to abrupt faults and non-Gaussian outliers. Signal-processing algorithms based on radial basis function (RBF) neural network and weighted recursive median (WRM) filters are explored for denoising simulated time series. The RBF neural network filter is developed using a K-means clustering algorithm and is much less computationally expensive to develop than feedforward neural networks trained using backpropagation. The nonlinear multimodal integer-programming problem of selecting optimal integer weights of the WRM filter is solved using genetic algorithm. Numerical results are obtained for helicopter rotor structural damage indicators based on simulated frequencies. Test signals consider low order polynomial growth of damage indicators with time to simulate gradual or incipient faults and step changes in the signal to simulate abrupt faults. Noise and outliers are added to the test signals. The WRM and RBF filters result in a noise reduction of 54 - 71 and 59 - 73% for the test signals considered in this study, respectively. Their performance is much better than the moving average FIR filter, which causes significant feature distortion and has poor outlier removal capabilities and shows the potential of soft computing methods for specific signal-processing applications.

Ab initio studies on the tri- and diphosphate fragments of adenosine triphosphate

Pyrophosphate prototypes such as methyl triphosphate and methyl diphosphate molecules in their different protonation states have been investigated at high levels of quantum chemical calculations. The optimized geometries, the thermochemistry of the hydrolysis and the molecular orbitals contributing to the high energy of these compounds have been analyzed. These investigations provide insights into the "high energy" character of ATP molecule. Further, the dependence of vibrational frequencies on the number of phosphate groups and the charged states has also been presented. These results can aid the interpretation of spectra obtained by experiments on complexes containing pyrophosphate prototypes.

New phase unwrapping strategy for rapid and dense 3D data acquisition in structured light approach

Sinusoidal structured light projection (SSLP) technique, specifically-phase stepping method, is in widespread use to obtain accurate, dense 3-D data. But, if the object under investigation possesses surface discontinuities, phase unwrapping (an intermediate step in SSLP) stage mandatorily require several additional images, of the object with projected fringes (of different spatial frequencies), as input to generate a reliable 3D shape. On the other hand, Color-coded structured light projection (CSLP) technique is known to require a single image as in put, but generates sparse 3D data. Thus we propose the use of CSLP in conjunction with SSLP to obtain dense 3D data with minimum number of images as input. This approach is shown to be significantly faster and reliable than temporal phase unwrapping procedure that uses a complete exponential sequence. For example, if a measurement with the accuracy obtained by interrogating the object with 32 fringes in the projected pattern is carried out with both the methods, new strategy proposed requires only 5 frames as compared to 24 frames required by the later method.

Structural, dielectric and ferroelectric properties of four-layer Aurivillius phase Na0.5La0.5Bi4Ti4O15

Monophasic Na0.5La0.5Bi4Ti4O15 powders were synthesized via the conventional solid-state reaction route. The X-ray powder diffraction (XRD), selected area electron diffraction (SAED) and high resolution transmission electron microscopy (HRTEM) studies carried out on the as synthesized powdered samples confirmed the phase to be a four-layer Aurivillius that crystallizes in an orthorhombic A2(1)am space group. The microstructure and the chemical composition of the sintered sample were examined by scanning electron microscope (SEM) equipped with an energy dispersive X-ray analyzer (EDX). The dielectric properties of the ceramics have been studied in the 27-700 degrees C temperature range at various frequencies (100 Hz to 1 MHz). A sharp dielectric anomaly was observed at 580 degrees C for all the frequencies corresponding to the ferroelectric to paraelectric phase transition. Saturated ferroelectric hysteresis loops were observed at 200 degrees C and the associated remnant polarization (P-r) and coercive field (E-c) were found to be 7.4 mu C/cm(2) and 34.8 kV/cm, respectively. AC conductivity analysis confirmed the existence of two different conduction mechanisms in the ferroelectric region. Activation energies calculated from the Arrhenius plots were similar to 0.24 eV and similar to 0.84 eV in the 300-450 degrees C and 450-580 degrees C temperature ranges, respectively. (C) 2010 Elsevier B.V. All rights reserved.

Infrared Spectra of Dimethylquinolines in the Gas Phase: Experiment and Theory

Infrared spectra of atmospherically important dimethylquinolines (DMQs), namely 2,4-DMQ, 2,6-DMQ, 2,7-DMQ, and 2,8-DMQ in the gas phase at 80 degrees C were recorded using a long variable path-length cell. DFT calculations were carried out to assign the bands in the experimentally observed spectra at the B3LYP/6-31G* level of theory. The spectral assignments particularly for the C-H stretching modes could not be made unambiguously using calculated anharmonic or scaled harmonic frequencies. To resolve this problem, a scaled force field method of assignment was used. Assignment of fundamental modes was confirmed by potential energy distributions (PEDs) of the normal modes derived by the scaled force fields using a modified version of the UMAT program in the QCPE package. We demonstrate that for large molecules such as the DMQs, the scaling of the force field is more effective in arriving at the correct assignment of the fundamentals for a quantitative vibrational analysis. An error analysis of the mean deviation of the calculated harmonic, anharmonic, and force field fitted frequencies from the observed frequency provides strong evidence for the correctness of the assignment.

Generalized asymptotic expansions for coupled wavenumbers in fluid-filled cylindrical shells

Analytical expressions are found for the coupled wavenumbers in an infinite fluid-filled cylindrical shell using the asymptotic methods. These expressions are valid for any general circumferential order (n).The shallow shell theory (which is more accurate at higher frequencies)is used to model the cylinder. Initially, the in vacua shell is dealt with and asymptotic expressions are derived for the shell wavenumbers in the high-and the low-frequency regimes. Next, the fluid-filled shell is considered. Defining a relevant fluid-loading parameter p, we find solutions for the limiting cases of small and large p. Wherever relevant, a frequency scaling parameter along with some ingenuity is used to arrive at an elegant asymptotic expression. In all cases.Poisson's ratio v is used as an expansion variable. The asymptotic results are compared with numerical solutions of the dispersion equation and the dispersion relation obtained by using the more general Donnell-Mushtari shell theory (in vacuo and fluid-filled). A good match is obtained. Hence, the contribution of this work lies in the extension of the existing literature to include arbitrary circumferential orders(n). (C) 2010 Elsevier Ltd. All rights reserved.

Uniparental DNA markers and forensic genetics in Finland

Over the years, a wide range of methods to verify identity have been developed. Molecular markers have been used for identification since the 1920s, commencing with blood types and culminating with the advent of DNA techniques in the 1980s. Identification is required by authorities in many occasions, e.g. in disputed paternity cases, identification of deceased, or crime investigation. To clarify maternal and paternal lineages, uniparental DNA markers in mtDNA and Y-chromosome can be utilized. These markers have several advantages: male specific Y-chromosome can be used to identify a male from a mixture of male and female cells, e.g. in rape cases. MtDNA is durable and has a high copy number, allowing analyses even from old or degraded samples. However, both markers are lineage-specific, not individualizing, and susceptible to genetic drift. Prior to the application of any DNA marker in forensic casework, it is of utmost importance to investigate its qualities and peculiarities in the target population. Earlier studies on the Finnish population have shown reduced variation in the Y-chromosome, but in mtDNA results have been ambiguous. The obtained results confirmed the low diversity in Y-chromosome in Finland. Detailed population analysis revealed large regional differences, and extremely reduced diversity especially in East Finland. Analysis of the qualities affecting Y-chromosomal short tandem repeat (Y-STR) variation and mutation frequencies, and search of new polymorphic markers resulted a set of Y-STRs with especially high diversity in Finland. Contrary to Y-chromosome, neither reduced diversity nor regional differences were found in mtDNA within Finland. In fact, mtDNA diversity was found similar to other European populations. The revealed peculiarities in the uniparental markers are a legacy of the Finnish population history. The obtained results challenge the traditional explanation which emphasizes relatively recent founder effects creating the observed east-west patterns. Uniparentally inherited markers, both mtDNA and Y-chromosome, are applicable for identification purposes in Finland. By adjusting the analysed Y marker set to meet the characteristics of Finnish population, Y-chromosomal diversity increases and the regional differentiation decreases, resulting increase in discrimination power and thus usefulness of Y-chromosomal analysis in forensic casework.

On the admittance of lipid bilayer membranes: Part I. Membrane-permeable ions

The modular formalism of Rangarajan [J. Electroanal. Chem., 55 (1974) 297] has been applied to the admittance of lipid bilayer membranes. The method leads to equations which clearly show the interrelations between the various partial processes involved in ion transport, and which allow examination of model assumptions without the need for a complete rederivation of the membrane admittance. Explicit expressions are given for both the continuum and single jump models. The former includes the ionic displacement component, important mostly at high frequencies.

On the admittance of lipid bilayer membranes: Part I. Membrane-permeable ions

The modular formalism of Rangarajan [J. Electroanal. Chem., 55 (1974) 297] has been applied to the admittance of lipid bilayer membranes. The method leads to equations which clearly show the interrelations between the various partial processes involved in ion transport, and which allow examination of model assumptions without the need for a complete rederivation of the membrane admittance. Explicit expressions are given for both the continuum and single jump models. The former includes the ionic displacement component, important mostly at high frequencies.

A.C. electrical conductivity of pure and doped potassium perchlorate

A.C. electrical conductivity of potassium perchlorate (KP) has been measured in the temperature range 25�325°C at frequencies ranging from 50�500 Hz using an automated technique. The results are interpreted in terms of a novel mechanism involving Schottky defects in the anion sublattice and Frenkel defects in the cation sublattice. Theconductivity behavior of KP is compared with literature data on similar low-symmetry systems containing polyatomic ions.