Identification of lipophilic flavones and flavonols by comparative HPLC, TLC and UV spectral analysis

The identification of lipophilic flavones and flavonols using a combination of high performance liquid chromatography, thin layer chromatography and UV spectral analysis is discussed. Data are provided for the flavones, apigenin, luteolin and tricetin and twelve of their methyl ethers, 8-hydroxyluteolin, 6-hydroxyluteolin and scutellarein and fourteen of their methyl ethers, and some 6,8-dihydroxyapigenin and 6,8-dihydroxyluteolin derivatives. Data for some forty two flavonols with extra 6- and/or 8-hydroxylation, mostly 6-hydroxykaempferol and quercetagetin derivatives, are also presented. The remaining compounds analysed include fourteen 5-deoxyflavones, four 5-methoxyflavones and five 5-deoxyflavonols plus further 5-hydroxylated flavones and flavonols without B-ring oxidation or with 2-, 5- or 6-hydroxylation. Copyright © 2003 John Wiley & Sons, Ltd.

Limit operators, collective compactness, and the spectral theory of infinite matrices

In the first half of this memoir we explore the interrelationships between the abstract theory of limit operators (see e.g. the recent monographs of Rabinovich, Roch and Silbermann (2004) and Lindner (2006)) and the concepts and results of the generalised collectively compact operator theory introduced by Chandler-Wilde and Zhang (2002). We build up to results obtained by applying this generalised collectively compact operator theory to the set of limit operators of an operator (its operator spectrum). In the second half of this memoir we study bounded linear operators on the generalised sequence space , where and is some complex Banach space. We make what seems to be a more complete study than hitherto of the connections between Fredholmness, invertibility, invertibility at infinity, and invertibility or injectivity of the set of limit operators, with some emphasis on the case when the operator is a locally compact perturbation of the identity. Especially, we obtain stronger results than previously known for the subtle limiting cases of and . Our tools in this study are the results from the first half of the memoir and an exploitation of the partial duality between and and its implications for bounded linear operators which are also continuous with respect to the weaker topology (the strict topology) introduced in the first half of the memoir. Results in this second half of the memoir include a new proof that injectivity of all limit operators (the classic Favard condition) implies invertibility for a general class of almost periodic operators, and characterisations of invertibility at infinity and Fredholmness for operators in the so-called Wiener algebra. In two final chapters our results are illustrated by and applied to concrete examples. Firstly, we study the spectra and essential spectra of discrete Schrödinger operators (both self-adjoint and non-self-adjoint), including operators with almost periodic and random potentials. In the final chapter we apply our results to integral operators on .

The troposphere-to-stratosphere transition in kinetic energy spectra and nonlinear spectral fluxes as seen in ECMWF analyses

Global horizontal wavenumber kinetic energy spectra and spectral fluxes of rotational kinetic energy and enstrophy are computed for a range of vertical levels using a T799 ECMWF operational analysis. Above 250 hPa, the kinetic energy spectra exhibit a distinct break between steep and shallow spectral ranges, reminiscent of dual power-law spectra seen in aircraft data and high-resolution general circulation models. The break separates a large-scale ‘‘balanced’’ regime in which rotational flow strongly dominates divergent flow and a mesoscale ‘‘unbalanced’’ regime where divergent energy is comparable to or larger than rotational energy. Between 230 and 100 hPa, the spectral break shifts to larger scales (from n 5 60 to n 5 20, where n is spherical harmonic index) as the balanced component of the flow preferentially decays. The location of the break remains fairly stable throughout the stratosphere. The spectral break in the analysis occurs at somewhat larger scales than the break seen in aircraft data. Nonlinear spectral fluxes defined for the rotational component of the flow maximize between about 300 and 200 hPa. Large-scale turbulence thus centers on the extratropical tropopause region, within which there are two distinct mechanisms of upscale energy transfer: eddy–eddy interactions sourcing the transient energy peak in synoptic scales, and zonal mean–eddy interactions forcing the zonal flow. A well-defined downscale enstrophy flux is clearly evident at these altitudes. In the stratosphere, the transient energy peak moves to planetary scales and zonal mean–eddy interactions become dominant.

Kraichnan–Leith–Batchelor similarity theory and two-dimensional inverse cascades

We study the scaling properties and Kraichnan–Leith–Batchelor (KLB) theory of forced inverse cascades in generalized two-dimensional (2D) fluids (α-turbulence models) simulated at resolution 8192x8192. We consider α=1 (surface quasigeostrophic flow), α=2 (2D Euler flow) and α=3. The forcing scale is well resolved, a direct cascade is present and there is no large-scale dissipation. Coherent vortices spanning a range of sizes, most larger than the forcing scale, are present for both α=1 and α=2. The active scalar field for α=3 contains comparatively few and small vortices. The energy spectral slopes in the inverse cascade are steeper than the KLB prediction −(7−α)/3 in all three systems. Since we stop the simulations well before the cascades have reached the domain scale, vortex formation and spectral steepening are not due to condensation effects; nor are they caused by large-scale dissipation, which is absent. One- and two-point p.d.f.s, hyperflatness factors and structure functions indicate that the inverse cascades are intermittent and non-Gaussian over much of the inertial range for α=1 and α=2, while the α=3 inverse cascade is much closer to Gaussian and non-intermittent. For α=3 the steep spectrum is close to that associated with enstrophy equipartition. Continuous wavelet analysis shows approximate KLB scaling ℰ(k)∝k−2 (α=1) and ℰ(k)∝k−5/3 (α=2) in the interstitial regions between the coherent vortices. Our results demonstrate that coherent vortex formation (α=1 and α=2) and non-realizability (α=3) cause 2D inverse cascades to deviate from the KLB predictions, but that the flow between the vortices exhibits KLB scaling and non-intermittent statistics for α=1 and α=2.

Calculating the ocean's mean dynamic topography from a mean sea surface and a geoid

In principle the global mean geostrophic surface circulation of the ocean can be diagnosed by subtracting a geoid from a mean sea surface (MSS). However, because the resulting mean dynamic topography (MDT) is approximately two orders of magnitude smaller than either of the constituent surfaces, and because the geoid is most naturally expressed as a spectral model while the MSS is a gridded product, in practice complications arise. Two algorithms for combining MSS and satellite-derived geoid data to determine the ocean’s mean dynamic topography (MDT) are considered in this paper: a pointwise approach, whereby the gridded geoid height field is subtracted from the gridded MSS; and a spectral approach, whereby the spherical harmonic coefficients of the geoid are subtracted from an equivalent set of coefficients representing the MSS, from which the gridded MDT is then obtained. The essential difference is that with the latter approach the MSS is truncated, a form of filtering, just as with the geoid. This ensures that errors of omission resulting from the truncation of the geoid, which are small in comparison to the geoid but large in comparison to the MDT, are matched, and therefore negated, by similar errors of omission in the MSS. The MDTs produced by both methods require additional filtering. However, the spectral MDT requires less filtering to remove noise, and therefore it retains more oceanographic information than its pointwise equivalent. The spectral method also results in a more realistic MDT at coastlines. 1. Introduction An important challenge in oceanography is the accurate determination of the ocean’s time-mean dynamic topography (MDT). If this can be achieved with sufficient accuracy for combination with the timedependent component of the dynamic topography, obtainable from altimetric data, then the resulting sum (i.e., the absolute dynamic topography) will give an accurate picture of surface geostrophic currents and ocean transports.

On integral equation and least squares methods for scattering by diffraction gratings

In this paper we consider the scattering of a plane acoustic or electromagnetic wave by a one-dimensional, periodic rough surface. We restrict the discussion to the case when the boundary is sound soft in the acoustic case, perfectly reflecting with TE polarization in the EM case, so that the total field vanishes on the boundary. We propose a uniquely solvable first kind integral equation formulation of the problem, which amounts to a requirement that the normal derivative of the Green's representation formula for the total field vanish on a horizontal line below the scattering surface. We then discuss the numerical solution by Galerkin's method of this (ill-posed) integral equation. We point out that, with two particular choices of the trial and test spaces, we recover the so-called SC (spectral-coordinate) and SS (spectral-spectral) numerical schemes of DeSanto et al., Waves Random Media, 8, 315-414 1998. We next propose a new Galerkin scheme, a modification of the SS method that we term the SS* method, which is an instance of the well-known dual least squares Galerkin method. We show that the SS* method is always well-defined and is optimally convergent as the size of the approximation space increases. Moreover, we make a connection with the classical least squares method, in which the coefficients in the Rayleigh expansion of the solution are determined by enforcing the boundary condition in a least squares sense, pointing out that the linear system to be solved in the SS* method is identical to that in the least squares method. Using this connection we show that (reflecting the ill-posed nature of the integral equation solved) the condition number of the linear system in the SS* and least squares methods approaches infinity as the approximation space increases in size. We also provide theoretical error bounds on the condition number and on the errors induced in the numerical solution computed as a result of ill-conditioning. Numerical results confirm the convergence of the SS* method and illustrate the ill-conditioning that arises.

Interference filters and coatings for mid-infrared astronomy (8-30µm)

The VISIR instrument for the European Southern Observatory (ESO) Very Large Telescope (VLT) is a thermal-infrared imager and spectrometer currently being developed by the French Service d'Astrophysique of CEA Saclay, and Dutch NFRA ASTRON Dwingeloo consortium. This cryogenic instrument will employ precision infrared bandpass filters in the N-( =7.5-14µm) and Q-( =16-28µm) band mid-IR atmospheric windows to study interstellar and circumstellar environments crucial for star and planetary formation theories. As the filters in these mid-IR wavelength ranges are of interest to many astronomical cryogenic instruments, a worldwide astronomical filter consortium was set up with participation from 12 differing institutes, each requiring instrument specific filter operating environments and optical metrology. This paper describes the design and fabrication methods used to manufacture these astronomical consortium filters, including the rationale for the selection of multilayer coating designs, temperature-dependant optical properties of the filter materials and FTIR spectral measurements showing the changes in passband and blocking performance on cooling to <50K. We also describe the development of a 7-14µm broadband antireflection coating deposited on Ge lenses and KRS-5 grisms for cryogenic operation at 40K

Infrared filters and coatings for the High Resolution Dynamics Limb Sounder (6-18µm)

This paper describes the spectral design and manufacture of the narrow bandpass filters and 6-18µm broadband antireflection coatings for the 21-channel NASA EOS-AURA High Resolution Dynamics Limb Sounder (HIRDLS). A method of combining the measured spectral characteristics of each filter and antireflection coating, together with the spectral response of the other optical elements in the instrument to obtain a predicted system throughput response is presented. The design methods used to define the filter and coating spectral requirements, choice of filter materials, multilayer designs and deposition techniques are discussed.

Synthesis and X-ray crystal structure of the copper(I) dicarboxylic acid complex [Cu(η1-bdoaH)(PPh3)3] (bdoaH2 = benzene-1,2- dioxyacetic acid)

The copper(II) complex [Cu(bdoa)(H2O)2] (bdoaH2 = benzene-1,2-dioxyacetic acid) reacts with triphenylphosphine (1:4 mol ratio) to give the colourless copper(I) complex [Cu(η1-bdoaH)(PPh3)3] (1) in good yield. The X-ray crystal structure of the complex shows the copper atom at the centre of a distorted tetrahedron, and is ligated by the phosphorus atoms of the three triphenylphosphines and one carboxylate oxygen atom of the bdoaH− ligand. Significant intermolecular hydrogen-bonding exists between the pendant carboxylate OH function of one molecule and the uncoordinated “ketonic” oxygen of a neighbouring molecule. Complex 1 is non-conducting in chloroform but ionizes readily in acetonitrile. The cyclic voltammogram of an acetonitrile solution of 1 shows a single irreversible anodic peak for the oxidation of the PPh3 ligands and the copper(I) centre, and a single irreversible cathodic peak for the reduction of the bdoaH− ion. IR and mass spectral data for 1 are given.

Absolute high spectral resolution measurements of surface solar radiation for detection of water vapour continuum absorption

Solar-pointing Fourier transform infrared (FTIR) spectroscopy offers the capability to measure both the fine scale and broadband spectral structure of atmospheric transmission simultaneously across wide spectral regions. It is therefore suited to the study of both water vapour monomer and continuum absorption behaviours. However, in order to properly address this issue, it is necessary to radiatively calibrate the FTIR instrument response. A solar-pointing high-resolution FTIR spectrometer was deployed as part of the ‘Continuum Absorption by Visible and Infrared radiation and its Atmospheric Relevance’ (CAVIAR) consortium project. This paper describes the radiative calibration process using an ultra-high-temperature blackbody and the consideration of the related influence factors. The result is a radiatively calibrated measurement of the solar irradiation at the ground across the IR region from 2000 to 10 000 cm−1 with an uncertainty of between 3.3 and 5.9 per cent. This measurement is shown to be in good general agreement with a radiative-transfer model. The results from the CAVIAR field measurements are being used in ongoing studies of atmospheric absorbers, in particular the water vapour continuum.

Structural variations in self-assembled coordination complexes of Zn(II) with hexamethylenetetramine and isomeric 2-, 3- and 4-nitrobenzoates

Three new zinc(II)-hexamethylenetetramine (hmt) complexes [Zn-2(4-nbz)(4)(mu(2)-hmt)(OH2)(hmt)] (1). [Zn-2(2-nbz)(4)(mu(2)-hmt)(2)](n) (2) and [Zn-3(3-nbz)(4)(mu(2)-hmt)(mu(2)-OH)(mu(3)-OH)](n) (3) with three isomeric nitrobenzoate, [4-nbz = 4-nitrobenzoate, 2-nbz = 2-nitrobenzoate and 3-nbz = 3-nitrobenzoate] have been synthesized and structurally characterized by X-ray crystallography. Their identities have also been established by elemental analysis: IR, NMR, UV-Vis and mass spectral studies. 1 is a dinuclear complex formed by bridging hmt with mu(2) coordinating mode. The geometry around the Zn centers in 1 is distorted tetrahedral. Paddle-wheel centrosymmetric Zn-2(2-nbz)(4) units of complex 2 are interconnected by mu(2)-hmt forming a one-dimensional chain with square-pyramidal geometries around the Zn centers. Compound 3 contains a mu(2)/mu(3)-hydroxido and mu(2)-hmt bridged 1D chain. In this complex, varied geometries around the Zn centers are observed viz, tetrahedral, square pyramidal and trigonal bipyramidal. Various weak forces, i.e. lone pair-pi, pi-pi and CH-pi interactions, play a key role in stabilizing the observed structures for complexes 1,2 and 3. This series of complexes demonstrates that although the nitro group does not coordinate to the metal center, its presence at the 2-, 3- or 4-position of the phenyl ring has a striking effect on the dimensionality as well as the structure of the resulted coordination polymers, probably due to the participation of the nitro group in 1.p.center dot center dot center dot pi and/or C-H center dot center dot center dot pi interactions.

Synthesis, characterization, crystal structure, and DNA-binding of ruthenium(II) complexes of heterocyclic nitrogen ligands resulting from a benzimidazole-based quinazoline derivative

The reaction of cis-[RuCl2(dmso)(4)] with [6-(2-pyridinyl)-5,6-dihydrobenzimidazo[1,2-c] quinazoline] (L) afforded in pure form a blue ruthenium(II) complex, [Ru(L-1)(2)] (1), where the original L changed to [2-(1H-benzoimidazol-2-yl)-phenyl]-pyridin-2-ylmethylene-amine (HL1). Treatment of RuCl3 center dot 3H(2)O with L in dry tetrahydrofuran in inert atmosphere led to a green ruthenium(II) complex, trans-[RuCl2(L-2)(2)] (2), where L was oxidized in situ to the neutral species 6-pyridin-yl-benzo[4,5]imidazo[1,2-c] quinazoline (L-2). Complex 2 was also obtained from the reaction of RuCl3 center dot 3H(2)O with L-2 in dry ethanol. Complexes 1 and 2 have been characterized by physico-chemical and spectroscopic tools, and 1 has been structurally characterized by single-crystal X-ray crystallography. The electrochemical behavior of the complexes shows the Ru(III)/Ru(II) couple at different potentials with quasi-reversible voltammograms. The interaction of these complexes with calf thymus DNA by using absorption and emission spectral studies allowed determination of the binding constant K-b and the linear Stern-Volmer quenching constant K-SV

Gaussian anamorphosis in the analysis step of the EnKF: a joint state-variable/observation approach

The analysis step of the (ensemble) Kalman filter is optimal when (1) the distribution of the background is Gaussian, (2) state variables and observations are related via a linear operator, and (3) the observational error is of additive nature and has Gaussian distribution. When these conditions are largely violated, a pre-processing step known as Gaussian anamorphosis (GA) can be applied. The objective of this procedure is to obtain state variables and observations that better fulfil the Gaussianity conditions in some sense. In this work we analyse GA from a joint perspective, paying attention to the effects of transformations in the joint state variable/observation space. First, we study transformations for state variables and observations that are independent from each other. Then, we introduce a targeted joint transformation with the objective to obtain joint Gaussianity in the transformed space. We focus primarily in the univariate case, and briefly comment on the multivariate one. A key point of this paper is that, when (1)-(3) are violated, using the analysis step of the EnKF will not recover the exact posterior density in spite of any transformations one may perform. These transformations, however, provide approximations of different quality to the Bayesian solution of the problem. Using an example in which the Bayesian posterior can be analytically computed, we assess the quality of the analysis distributions generated after applying the EnKF analysis step in conjunction with different GA options. The value of the targeted joint transformation is particularly clear for the case when the prior is Gaussian, the marginal density for the observations is close to Gaussian, and the likelihood is a Gaussian mixture.

Nightside studies of coherent HF Radar spectral width behaviour

A previous case study found a relationship between high spectral width measured by the CUTLASS Finland HF radar and elevated electron temperatures observed by the EISCAT and ESR incoherent scatter radars in the postmidnight sector of magnetic local time. This paper expands that work by briefly re-examining that interval and looking in depth at two further case studies. In all three cases a region of high HF spectral width (>200 ms−1) exists poleward of a region of low HF spectral width (<200 ms^{−1}). Each case, however, occurs under quite different geomagnetic conditions. The original case study occurred during an interval with no observed electrojet activity, the second study during a transition from quiet to active conditions with a clear band of ion frictional heating indicating the location of the flow reversal boundary, and the third during an isolated substorm. These case studies indicate that the relationship between elevated electron temperature and high HF radar spectral width appears on closed field lines after 03:00 magnetic local time (MLT) on the nightside. It is not clear whether the same relationship would hold on open field lines, since our analysis of this relationship is restricted in latitude. We find two important properties of high spectral width data on the nightside. Firstly the high spectral width values occur on both open and closed field lines, and secondly that the power spectra which exhibit high widths are both single-peak and multiple-peak. In general the regions of high spectral width (>200 ms−1) have more multiple-peak spectra than the regions of low spectral widths whilst still maintaining a majority of single-peak spectra. We also find that the region of ion frictional heating is collocated with many multiplepeak HF spectra. Several mechanisms for the generation of high spectral width have been proposed which would produce multiple-peak spectra, these are discussed in relation to the data presented here. Since the regions of high spectral width are observed both on closed and open field lines the use of the boundary between low and high spectral width as an ionospheric proxy for the open/closed field line boundary is not a simple matter, if indeed it is possible at all.

Midday auroral breakup events and related energy and momentum transfer from the magnetosheath

Combined observations by meridian-scanning photometers, all-sky auroral TV camera and the EISCAT radar permitted a detailed analysis of the temporal and spatial development of the midday auroral breakup phenomenon and the related ionospheric ion flow pattern within the 71°–75° invariant latitude radar field of view. The radar data revealed dominating northward and westward ion drifts, of magnitudes close to the corresponding velocities of the discrete, transient auroral forms, during the two different events reported here, characterized by IMF |BY/BZ| < 1 and > 2, respectively (IMF BZ between −8 and −3 nT and BY > 0). The spatial scales of the discrete optical events were ∼50 km in latitude by ∼500 km in longitude, and their lifetimes were less than 10 min. Electric potential enhancements with peak values in the 30–50 kV range are inferred along the discrete arc in the IMF |BY/BZ| < 1 case from the optical data and across the latitudinal extent of the radar field of view in the |BY/BZ| > 2 case. Joule heat dissipation rates in the maximum phase of the discrete structures of ∼ 100 ergs cm−2 s−1 (0.1 W m−2) are estimated from the photometer intensities and the ion drift data. These observations combined with the additional characteristics of the events, documented here and in several recent studies (i.e., their quasi-periodic nature, their motion pattern relative to the persistent cusp or cleft auroral arc, the strong relationship with the interplanetary magnetic field and the associated ion drift/E field events and ground magnetic signatures), are considered to be strong evidence in favour of a transient, intermittent reconnection process at the dayside magnetopause and associated energy and momentum transfer to the ionosphere in the polar cusp and cleft regions. The filamentary spatial structure and the spectral characteristics of the optical signature indicate associated localized ˜1-kV potential drops between the magnetopause and the ionosphere during the most intense auroral events. The duration of the events compares well with the predicted characteristic times of momentum transfer to the ionosphere associated with the flux transfer event-related current tubes. It is suggested that, after this 2–10 min interval, the sheath particles can no longer reach the ionosphere down the open flux tube, due to the subsequent super-Alfvénic flow along the magnetopause, conductivities are lower and much less momentum is extracted from the solar wind by the ionosphere. The recurrence time (3–15 min) and the local time distribution (∼0900–1500 MLT) of the dayside auroral breakup events, combined with the above information, indicate the important roles of transient magnetopause reconnection and the polar cusp and cleft regions in the transfer of momentum and energy between the solar wind and the magnetosphere.