Coherent EISCAT Svalbard Radar spectra from the dayside cusp/cleft and their implications for transient field-aligned currents

Naturally enhanced incoherent scatter spectra from the vicinity of the dayside cusp/cleft, interpreted as being due to plasma turbulence driven by short bursts of intense field-aligned current, are compared with high-resolution narrow-angle auroral images and meridian scanning photometer data. Enhanced spectra have been observed on many occasions in association with nightside aurora, but there has been only one report of such spectra seen in the cusp/cleft region. Narrow-angle images show considerable change in the aurora on timescales shorter than the 10-s radar integration period, which could explain spectra observed with both ion lines simultaneously enhanced. Enhanced radar spectra are generally seen inside or beside regions of 630-nm auroral emission, indicative of sharp F region conductivity gradients, but there appears also to be a correlation with dynamic, small-scale auroral forms of order 100 m and less in width.

Analysis of incoherent scatter spectra from non-Maxwellian plasma

Incoherent scatter data from non-thermal F-region ionospheric plasma are analysed, using theoretical spectra predicted by Raman et al. It is found that values of the semi-empirical drift parameter D∗, associated with deviations of the ion velocity distribution from a Maxwellian, and the plasma temperatures can be rigorously deduced (the results being independent of the path of iteration) if the angle between the line-of-sight and the geomagnetic field is larger than about 15–20 degrees. For small aspect angles, the deduced value of the average (or 3-D) ion temperature remains ambiguous and the analysis is restricted to the determination of the line-of-sight temperature because the theoretical spectrum is insensitive to non-thermal effects when the plasma is viewed along directions almost parallel to the magnetic field. This limitation is expected to apply to any realistic model of the ion velocity distribution, and its consequences are discussed. Fit strategies which allow for mixed ion composition are also considered. Examples of fits to data from various EISCAT observing programmes are presented.

1H-13C HSQC NMR spectroscopy for estimating procyanidin/prodelphinidin and cis/trans-flavan-3-ol ratios of condensed tannin samples: correlation with thiolysis

Studies with a diverse array of 22 purified condensed tannin (CT) samples from nine plant species demonstrated that procyanidin/prodelphinidin (PC/PD) and cis/trans-flavan-3-ol ratios can be appraised by 1H-13C HSQC NMR spectroscopy. The method was developed from samples containing 44 to ~100% CT, PC/PD ratios ranging from 0/100 to 99/1, and cis/trans ratios from 58/42 to 95/5 as determined by thiolysis with benzyl mercaptan. Integration of cross-peak contours of H/C-6' signals from PC and of H/C-2',6' signals from PD yielded nuclei adjusted estimates that were highly correlated with PC/PD ratios obtained by thiolysis (R2 = 0.99). Cis/trans-flavan-3-ol ratios, obtained by integration of the respective H/C-4 cross-peak contours, were also related to determinations made by thiolysis (R2 = 0.89). Overall, 1H-13C HSQC NMR spectroscopy appears to be a viable alternative to thiolysis for estimating PC/PD and cis/trans ratios of CT, if precautions are taken to avoid integration of cross-peak contours of contaminants.

Application of complex extreme learning machine to multiclass classification problems with high dimensionality: a THz spectra classification problem

We extend extreme learning machine (ELM) classifiers to complex Reproducing Kernel Hilbert Spaces (RKHS) where the input/output variables as well as the optimization variables are complex-valued. A new family of classifiers, called complex-valued ELM (CELM) suitable for complex-valued multiple-input–multiple-output processing is introduced. In the proposed method, the associated Lagrangian is computed using induced RKHS kernels, adopting a Wirtinger calculus approach formulated as a constrained optimization problem similarly to the conventional ELM classifier formulation. When training the CELM, the Karush–Khun–Tuker (KKT) theorem is used to solve the dual optimization problem that consists of satisfying simultaneously smallest training error as well as smallest norm of output weights criteria. The proposed formulation also addresses aspects of quaternary classification within a Clifford algebra context. For 2D complex-valued inputs, user-defined complex-coupled hyper-planes divide the classifier input space into four partitions. For 3D complex-valued inputs, the formulation generates three pairs of complex-coupled hyper-planes through orthogonal projections. The six hyper-planes then divide the 3D space into eight partitions. It is shown that the CELM problem formulation is equivalent to solving six real-valued ELM tasks, which are induced by projecting the chosen complex kernel across the different user-defined coordinate planes. A classification example of powdered samples on the basis of their terahertz spectral signatures is used to demonstrate the advantages of the CELM classifiers compared to their SVM counterparts. The proposed classifiers retain the advantages of their ELM counterparts, in that they can perform multiclass classification with lower computational complexity than SVM classifiers. Furthermore, because of their ability to perform classification tasks fast, the proposed formulations are of interest to real-time applications.

Wave spectra assimilation in typhoon wave modeling for the East China Sea

The East China Sea is a hot area for typhoon waves to occur. A wave spectra assimilation model has been developed to predict the typhoon wave more accurately and operationally. This is the first time where wave data from Taiwan have been used to predict typhoon wave along the mainland China coast. The two-dimensional spectra observed in Taiwan northeast coast modify the wave field output by SWAN model through the technology of optimal interpolation (OI) scheme. The wind field correction is not involved as it contributes less than a quarter of the correction achieved by assimilation of waves. The initialization issue for assimilation is discussed. A linear evolution law for noise in the wave field is derived from the SWAN governing equations. A two-dimensional digital low-pass filter is used to obtain the initialized wave fields. The data assimilation model is optimized during the typhoon Sinlaku. During typhoons Krosa and Morakot, data assimilation significantly improves the low frequency wave energy and wave propagation direction in Taiwan coast. For the far-field region, the assimilation model shows an expected ability of improving typhoon wave forecast as well, as data assimilation enhances the low frequency wave energy. The proportion of positive assimilation indexes is over 81% for all the periods of comparison. The paper also finds that the impact of data assimilation on the far-field region depends on the state of the typhoon developing and the swell propagation direction.

The interplay of metal-atom ordering, Fermi leveltuning and thermoelectric properties in cobalt shandites Co3M2S2 (M = Sn, In)

A combination of structural, physical and computational techniques including powder X-ray and neutron diffraction, SQUID magnetometry, electrical and thermal transport measurements, DFT calculations and 119Sn Mössbauer and X-ray photoelec-tron spectroscopies has been applied to Co3Sn2-xInxS2 (0 ≤ x ≤ 2) in an effort to understand the relationship between metal-atom ordering and physical properties as the Fermi level is systematically varied. Whilst solid solution behavior is found throughout the composition region, powder neutron diffraction reveals that indium preferentially occupies an inter-layer site over an alternative kagome-like intra-layer site. DFT calculations indicate that this ordering, which leads to a lowering of energy, is related to the dif-fering bonding properties of tin and indium. Spectroscopic data suggest that throughout the composition range 0 ≤ x ≤ 2, all ele-ments adopt oxidation states that are significantly reduced from expectations based on formal charges. Chemical substitution ena-bles the electrical transport properties to be controlled through tuning of the Fermi level within a region of the density of states, which comprises narrow bands of predominantly Co d-character. This leads to a compositionally-induced double metal-to-semiconductor-to-metal transition. The marked increase in the Seebeck coefficient as the semiconducting region is approached leads to a substantial improvement in the thermoelectric figure of merit, ZT, which exhibits a maximum of ZT = 0.32 at 673 K. At 425 K, the figure of merit for phases in the region 0.8 ≤ x ≤ 0.85 is amongst the highest reported for sulphide phases, suggesting these materials may have applications in low-grade waste heat recovery.

Calcium-mediated binding of DNA to 1,2-distearoyl-sn-glycero-3-phosphocholine-containing mixed lipid monolayers

The calcium-mediated interaction of DNA with monolayers of the non-toxic, zwitterionic phospholipid, 1,2-distearoyl-sn-glycero-3-phosphocholine when mixed with 50 mol% of a second lipid, either the zwitteronic 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine or neutral cholesterol was investigated using a combination of surface pressure-area isotherms, Brewster angle microscopy, external reflectance Fourier transform infrared spectroscopy and specular neutron reflectivity in combination with contrast variation. When calcium and DNA were both present in the aqueous subphase, changes were observed in the compression isotherms as well as the surface morphologies of the mixed lipid monolayers. In the presence of calcium and DNA, specular neutron reflectivity showed that directly underneath the head groups of the lipids comprising the monolayers, DNA occupied a layer comprising approximately 13 and 18% v/v DNA for the 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine and cholesterol-containing monolayers, respectively. The volume of the corresponding layer for 1,2-distearoyl-sn-glycero-3-phosphocholine only containing monolayers was ∼15% v/v DNA. Furthermore regardless of the presence and nature of the second lipid and the surface pressure of the monolayer, the specular neutron reflectivity experiments showed that the DNA-containing layer was 20–27 Å thick, suggesting the presence of a well-hydrated layer of double-stranded DNA. External reflectance Fourier transform infrared studies confirmed the presence of double stranded DNA, and indicated that the strands are in the B-form conformation. The results shed light on the interaction between lipids and nucleic acid cargo as well as the role of a second lipid in lipid-based carriers for drug delivery.

Electronic structure of Pd multi-layers on Re(0001): the role of charge transfer

Understanding the origin of the properties of metal-supported metal thin films is important for the rational design of bimetallic catalysts and other applications, but it is generally difficult to separate effects related to strain from those arising from interface interactions. Here we use density functional (DFT) theory to examine the structure and electronic behavior of few-layer palladium films on the rhenium (0001) surface, where there is negligible interfacial strain and therefore other effects can be isolated. Our DFT calculations predict stacking sequences and interlayer separations in excellent agreement with quantitative low-energy electron diffraction experiments. By theoretically simulating the Pd core-level X-ray photoemission spectra (XPS) of the films, we are able to interpret and assign the basic features of both low-resolution and high-resolution XPS measurements. The core levels at the interface shift to more negative energies, rigidly following the shifts in the same direction of the valence d-band center. We demonstrate that the valence band shift at the interface is caused by charge transfer from Re to Pd, which occurs mainly to valence states of hybridized s-p character rather than to the Pd d-band. Since the d-band filling is roughly constant, there is a correlation between the d-band center shift and its bandwidth. The resulting effect of this charge transfer on the valence d-band is thus analogous to the application of a lateral compressive strain on the adlayers. Our analysis suggests that charge transfer should be considered when describing the origin of core and valence band shifts in other metal / metal adlayer systems.

Surface chemistry of alanine on Ni{111}

The adsorption of L-alanine on Ni{111} has been studied as a 10 model of enantioselective heterogeneous catalysts. Synchrotron-based X-ray 11 photoelectron spectroscopy and near-edge X-ray absorption fine structure 12 (NEXAFS) spectroscopy were used to determine the chemical state, bond 13 coordination, and out-of-plane orientation of the molecule on the surface. 14 Alanine adsorbs in anionic and zwitterionic forms between 250 and ≈320 K. 15 NEXAFS spectra exhibit a strong angular dependence of the π* resonance 16 associated with the carboxylate group, which is compatible with two distinct 17 orientations with respect to the surface corresponding to the bidentate and 18 tridentate binding modes. Desorption and decomposition begin together at 19 ≈300 K, with decomposition occurring in a multistep process up to ≈450 K. Comparison with previous studies of amino acid 20 adsorption on metal surfaces shows that this is among the lowest decomposition temperatures found so far and lower than typical 21 temperatures used for hydrogenation reactions where modified Ni catalysts are used.

Using NMR-based metabolomics to evaluate postprandial urinary responses following consumption of minimally processed wheat bran or wheat aleurone by men and women

Wheat bran, and especially wheat aleurone fraction, are concentrated sources of a wide range of components which may contribute to the health benefits associated with higher consumption of whole-grain foods. This study used NMR metabolomics to evaluate urine samples from baseline at one and two hours postprandially, following the consumption of minimally processed bran, aleurone or control by 14 participants (7 Females; 7 Males) in a randomized crossover trial. The methodology discriminated between the urinary responses of control, and bran and aleurone, but not between the two fractions. Compared to control, consumption of aleurone or bran led to significantly and substantially higher urinary concentrations of lactate, alanine, N-acetylaspartate acid and N-acetylaspartylglutamate and significantly and substantially lower urinary betaine concentrations at one and two hours postprandially. There were sex related differences in urinary metabolite profiles with generally higher hippurate and citrate and lower betaine in females compared to males. Overall, this postprandial study suggests that acute consumption of bran or aleurone is associated with a number of physiological effects that may impact on energy metabolism and which are consistent with longer term human and animal metabolomic studies that used whole-grain wheat diets or wheat fractions.

Internal nanoparticle structure of temperature-responsive self-assembled PNIPAM-b-PEG-b-PNIPAM triblock copolymers in aqueous solutions: NMR, SANS and light scattering studies

In this study we report detailed information on the internal structure of PNIPAM-b-PEG-b-PNIPAM nanoparticles formed from self-assembly in aqueous solutions upon increase in temperature. NMR spectroscopy, light scattering and small-angle neutron scattering (SANS) were used to monitor different stages of nanoparticle formation as a function of temperature, providing insight into the fundamental processes involved. The presence of PEG in a copolymer structure significantly affects the formation of nanoparticles, making their transition to occur over a broader temperature range. The crucial parameter that controls the transition is the ratio of PEG/PNIPAM. For pure PNIPAM, the transition is sharp; the higher the PEG/PNIPAM ratio results in a broader transition. This behavior is explained by different mechanisms of PNIPAM block incorporation during nanoparticle formation at different PEG/PNIPAM ratios. Contrast variation experiments using SANS show that the structure of nanoparticles above cloud point temperatures for PNIPAM-b-PEG-b-PNIPAM copolymers is drastically different from the structure of PNIPAM mesoglobules. In contrast with pure PNIPAM mesoglobules, where solid-like particles and chain network with a mesh size of 1-3 nm are present; nanoparticles formed from PNIPAM-b-PEG-b-PNIPAM copolymers have non-uniform structure with “frozen” areas interconnected by single chains in Gaussian conformation. SANS data with deuterated “invisible” PEG blocks imply that PEG is uniformly distributed inside of a nanoparticle. It is kinetically flexible PEG blocks which affect the nanoparticle formation by prevention of PNIPAM microphase separation.

Predicting spectral features in galaxy spectra from broad-band photometry

We explore the prospects of predicting emission-line features present in galaxy spectra given broad-band photometry alone. There is a general consent that colours, and spectral features, most notably the 4000 angstrom break, can predict many properties of galaxies, including star formation rates and hence they could infer some of the line properties. We argue that these techniques have great prospects in helping us understand line emission in extragalactic objects and might speed up future galaxy redshift surveys if they are to target emission-line objects only. We use two independent methods, Artificial Neural Networks (based on the ANNz code) and Locally Weighted Regression (LWR), to retrieve correlations present in the colour N-dimensional space and to predict the equivalent widths present in the corresponding spectra. We also investigate how well it is possible to separate galaxies with and without lines from broad-band photometry only. We find, unsurprisingly, that recombination lines can be well predicted by galaxy colours. However, among collisional lines some can and some cannot be predicted well from galaxy colours alone, without any further redshift information. We also use our techniques to estimate how much information contained in spectral diagnostic diagrams can be recovered from broad-band photometry alone. We find that it is possible to classify active galactic nuclei and star formation objects relatively well using colours only. We suggest that this technique could be used to considerably improve redshift surveys such as the upcoming Fibre Multi Object Spectrograph (FMOS) survey and the planned Wide Field Multi Object Spectrograph (WFMOS) survey.

Nuclear and extended spectra of NGC 1068-I. Hints from near-infrared spectroscopy

We report the first simultaneous zJHK spectroscopy on the archetypical Seyfert 2 galaxy NGC 1068 covering the wavelength region 0.9-2.4 mu m. The slit, aligned in the north-south direction and centred in the optical nucleus, maps a region 300 pc in radius at subarcsec resolution, with a spectral resolving power of 360 km s-1. This configuration allows us to study the physical properties of the nuclear gas including that of the north side of the ionization cone, map the strong excess of continuum emission in the K band and attributed to dust and study the variations, both in flux and profile, in the emission lines. Our results show the following. (1) Mid- to low-ionization emission lines are split into two components, whose relative strengths vary with the position along the slit and seem to be correlated with the jet. (2) The coronal lines are single-peaked and are detected only in the central few hundred of pc from the nucleus. (3) The absorption lines indicate the presence of intermediate age stellar population, which might be a significant contributor to the continuum in the near-IR spectra. (4) Through some simple photoionization models we find photoionization as the main mechanism powering the emitting gas. (5) Calculations using stellar features point to a mass concentration inside the 100-200 pc of about 1010 M(circle dot).

Nuclear and extended spectra of NGC 1068-II. Near-infrared stellar population synthesis

We performed stellar population synthesis on the nuclear and extended regions of NGC 1068 by means of near-infrared spectroscopy to disentangle their spectral energy distribution components. This is the first time that such a technique is applied to the whole 0.8-2.4 mu m wavelength interval in this galaxy. NGC 1068 is one of the nearest and probably the most studied Seyfert 2 galaxy, becoming an excellent laboratory to study the interaction between black holes, the jets that they can produce and the medium in which they propagate. Our main result is that traces of young stellar population are found at similar to 100 pc south of the nucleus. The contribution of a power-law continuum in the centre is about 25 per cent, which is expected if the light is scattered from a Seyfert 1 nucleus. We find peaks in the contribution of the featureless continuum about 100-150 pc from the nucleus on both sides. They might be associated with regions where the jet encounters dense clouds. Further support to this scenario is given by the peaks of hot dust distribution found around these same regions and the H(2) emission-line profile, leading us to propose that the peaks might be associated to regions where stars are being formed. Hot dust also has an important contribution to the nuclear region, reinforcing the idea of the presence of a dense, circumnuclear torus in this galaxy. Cold dust appears mostly in the south direction, which supports the view that the south-west emission is behind the plane of the galaxy and is extinguished very likely by dust in the plane. Intermediate-age stellar population contributes significantly to the continuum, especially in the inner 200 pc.