Hydrogen-bond assisted stabilization of the less favored conformation of a tridentate Schiff base ligand in dinuclear nickel(II) complex: an experimental and theoretical study

The Schiff base ligand, HL (2-[1-(3-methylamino-propylimino)-ethyl]-phenol), the 1:1 condensation product of 2-hydroxy acetophenone and N-methyl-1,3-diaminopropane, has been synthesized and characterized by X-ray crystallography as the perchlorate salt [H2L]ClO4 (1). The structure consists of discrete [H2L](+) cations and perchlorate anions. Two dinuclear Ni-II complexes, [Ni2L2(NO2)(2)] (2), [Ni2L2(NO3)(2)] (3) have been synthesized using this ligand and characterized by single crystal X-ray analyses. Complexes 2 and 3 are centrosymmetric dimers in which the Ni-II ions are in distorted fac- and mer-octahedral environments, respectively, bridged by two mu(2)-phenolate ions of deprotonated ligand, L. The plane of the phenyl rings and the Ni2O2 basal plane are nearly coplanar in 2 but almost perpendicular in 3. We have studied and explained this different behavior using high level DFT calculations (RI-BP86/def2-TZVP level of theory). The conformation observed in 3, which is energetically less favorable, is stabilized via intermolecular non-covalent interactions. Under the excitation of ultraviolet light, characteristic fluorescence of compound 1 was observed; by comparison fluorescence intensity decreases in case of compound 3 and completely quenched in compound 2.

Necessary and sufficient conditions for realizability of point processes

We give necessary and sufficient conditions for a pair of (generali- zed) functions 1(r1) and 2(r1, r2), ri 2X, to be the density and pair correlations of some point process in a topological space X, for ex- ample, Rd, Zd or a subset of these. This is an infinite-dimensional version of the classical “truncated moment” problem. Standard tech- niques apply in the case in which there can be only a bounded num- ber of points in any compact subset of X. Without this restriction we obtain, for compact X, strengthened conditions which are necessary and sufficient for the existence of a process satisfying a further re- quirement—the existence of a finite third order moment. We general- ize the latter conditions in two distinct ways when X is not compact.

Female chromosomes in cockerel ejaculates

We describe a polymerase chain reaction which amplifies part of the Eco RI repeat unit of the fowl W chromosome. The resulting 447 bp fragment enables DNA from female birds to be identified. The composition of this DNA is confirmed by a nested polymerase chain reaction which specifically amplifies a known internal 263 bp region in this fragment. Using this technique it is possible to follow the fate of female cells in male germline chimaeras. The polymerase chain reaction fragment can be traced in cells of the embryonic and hatchling gonad and in adult sperm implying that cells containing the W chromosome are capable of being processed through the avian testis.

Synthesis and incorporation into cyclic peptides of tolan amino acids and their hydrogenated congeners: construction of an array of A–B-loop mimetics of the Cε3 domain of human IgE

The disruption of the human immunolobulin E–high affinity receptor I (IgE–FcεRI) protein–protein interaction (PPI) is a validated strategy for the development of anti asthma therapeutics. Here, we describe the synthesis of an array of conformationally constrained cyclic peptides based on an epitope of the A–B loop within the Cε3 domain of IgE. The peptides contain various tolan (i.e., 1,2-biarylethyne) amino acids and their fully and partially hydrogenated congeners as conformational constraints. Modest antagonist activity (IC50 660 μM) is displayed by the peptide containing a 2,2′-tolan, which is the one predicted by molecular modeling to best mimic the conformation of the native A–B loop epitope in IgE.

On the momentum fluxes associated with mountain waves in directionally sheared flows

The direct impact of mountain waves on the atmospheric circulation is due to the deposition of wave momentum at critical levels, or levels where the waves break. The first process is treated analytically in this study within the framework of linear theory. The variation of the momentum flux with height is investigated for relatively large shears, extending the authors’ previous calculations of the surface gravity wave drag to the whole atmosphere. A Wentzel–Kramers–Brillouin (WKB) approximation is used to treat inviscid, steady, nonrotating, hydrostatic flow with directional shear over a circular mesoscale mountain, for generic wind profiles. This approximation must be extended to third order to obtain momentum flux expressions that are accurate to second order. Since the momentum flux only varies because of wave filtering by critical levels, the application of contour integration techniques enables it to be expressed in terms of simple 1D integrals. On the other hand, the momentum flux divergence (which corresponds to the force on the atmosphere that must be represented in gravity wave drag parameterizations) is given in closed analytical form. The momentum flux expressions are tested for idealized wind profiles, where they become a function of the Richardson number (Ri). These expressions tend, for high Ri, to results by previous authors, where wind profile effects on the surface drag were neglected and critical levels acted as perfect absorbers. The linear results are compared with linear and nonlinear numerical simulations, showing a considerable improvement upon corresponding results derived for higher Ri.

Mountain waves in two-layer sheared flows: Critical-level effects, wave reflection, and drag enhancement

Internal gravity waves generated in two-layer stratified shear flows over mountains are investigated here using linear theory and numerical simulations. The impact on the gravity wave drag of wind profiles with constant unidirectional or directional shear up to a certain height and zero shear above, with and without critical levels, is evaluated. This kind of wind profile, which is more realistic than the constant shear extending indefinitely assumed in many analytical studies, leads to important modifications in the drag behavior due to wave reflection at the shear discontinuity and wave filtering by critical levels. In inviscid, nonrotating, and hydrostatic conditions, linear theory predicts that the drag behaves asymmetrically for backward and forward shear flows. These differences primarily depend on the fraction of wavenumbers that pass through their critical level before they are reflected by the shear discontinuity. If this fraction is large, the drag variation is not too different from that predicted for an unbounded shear layer, while if it is small the differences are marked, with the drag being enhanced by a considerable factor at low Richardson numbers (Ri). The drag may be further enhanced by nonlinear processes, but its qualitative variation for relatively low Ri is essentially unchanged. However, nonlinear processes seem to interact constructively with shear, so that the drag for a noninfinite but relatively high Ri is considerably larger than the drag without any shear at all.

A linear model of gravity wave drag for hydrostatic sheared flow over elliptical mountains

An analytical model of orographic gravity wave drag due to sheared flow past elliptical mountains is developed. The model extends the domain of applicability of the well-known Phillips model to wind profiles that vary relatively slowly in the vertical, so that they may be treated using a WKB approximation. The model illustrates how linear processes associated with wind profile shear and curvature affect the drag force exerted by the airflow on mountains, and how it is crucial to extend the WKB approximation to second order in the small perturbation parameter for these effects to be taken into account. For the simplest wind profiles, the normalized drag depends only on the Richardson number, Ri, of the flow at the surface and on the aspect ratio, γ, of the mountain. For a linear wind profile, the drag decreases as Ri decreases, and this variation is faster when the wind is across the mountain than when it is along the mountain. For a wind that rotates with height maintaining its magnitude, the drag generally increases as Ri decreases, by an amount depending on γ and on the incidence angle. The results from WKB theory are compared with exact linear results and also with results from a non-hydrostatic nonlinear numerical model, showing in general encouraging agreement, down to values of Ri of order one.

Resonant gravity-wave drag enhancement in linear stratified flow over mountains

High-drag states produced in stratified flow over a 2D ridge and an axisymmetric mountain are investigated using a linear, hydrostatic, analytical model. A wind profile is assumed where the background velocity is constant up to a height z1 and then decreases linearly, and the internal gravity-wave solutions are calculated exactly. In flow over a 2D ridge, the normalized surface drag is given by a closed-form analytical expression, while in flow over an axisymmetric mountain it is given by an expression involving a simple 1D integral. The drag is found to depend on two dimensionless parameters: a dimensionless height formed with z_1, and the Richardson number, Ri, in the shear layer. The drag oscillates as z_1 increases, with a period of half the hydrostatic vertical wavelength of the gravity waves. The amplitude of this modulation increases as Ri decreases. This behaviour is due to wave reflection at z_1. Drag maxima correspond to constructive interference of the upward- and downward-propagating waves in the region z < z_1, while drag minima correspond to destructive interference. The reflection coefficient at the interface z = z_1 increases as Ri decreases. The critical level, z_c, plays no role in the drag amplification. A preliminary numerical treatment of nonlinear effects is presented, where z_c appears to become more relevant, and flow over a 2D ridge qualitatively changes its character. But these effects, and their connection with linear theory, still need to be better understood.

An analytical model of mountain wave drag for wind profiles with shear and curvature

An analytical model is developed to predict the surface drag exerted by internal gravity waves on an isolated axisymmetric mountain over which there is a stratified flow with a velocity profile that varies relatively slowly with height. The model is linear with respect to the perturbations induced by the mountain, and solves the Taylor–Goldstein equation with variable coefficients using a Wentzel–Kramers–Brillouin (WKB) approximation, formally valid for high Richardson numbers, Ri. The WKB solution is extended to a higher order than in previous studies, enabling a rigorous treatment of the effects of shear and curvature of the wind profile on the surface drag. In the hydrostatic approximation, closed formulas for the drag are derived for generic wind profiles, where the relative magnitude of the corrections to the leading-order drag (valid for a constant wind profile) does not depend on the detailed shape of the orography. The drag is found to vary proportionally to Ri21, decreasing as Ri decreases for a wind that varies linearly with height, and increasing as Ri decreases for a wind that rotates with height maintaining its magnitude. In these two cases the surface drag is predicted to be aligned with the surface wind. When one of the wind components varies linearly with height and the other is constant, the surface drag is misaligned with the surface wind, especially for relatively small Ri. All these results are shown to be in fairly good agreement with numerical simulations of mesoscale nonhydrostatic models, for high and even moderate values of Ri.

The coupled model predictability of the Western North Pacific summer monsoon with different leading times

Leading time length is an important issue for modeling seasonal forecasts. In this study, a comparison of the interannual predictability of the Western North Pacific (WNP) summer monsoon between different leading months was performed by using one-, four-, and seven-month lead retrospective forecasts (hindcasts) of four coupled models from Ensembles-Based Predictions of Climate Changes and Their Impacts (ENSEMBLES) for the period of 1960-2005. It is found that the WNP summer anomalies, including lower-tropospheric circulation and precipitation anomalies, can be well predicted for all these leading months. The accuracy of the four-month lead prediction is only slightly weaker than that of the one-month lead prediction, although the skill decreases with the increase of leading months.

Wave-breaking characteristics of midlatitude blocking

In this article, Northern Hemisphere winter midlatitude blocking is analysed through its wave-breaking characteristics. Rossby wave breaking is identified as a key process in blocking occurrence, as it provides the mechanism for the meridional reversal pattern typical of blocking. Two indices are designed to detect the major properties of wave breaking, i.e. the orientation (cyclonic/anticyclonic–direction of breaking or DB index) and the relative contribution of air masses (warm/cold–relative intensity or RI index). The use of the DB index differentiates between the anticyclonic cases over Europe and Asia and the cyclonic events over the oceanic basins. One of the three regions displaying cyclonic type was found over the Atlantic Ocean, the other two being over the Pacific Ocean. The first of these is located over the western side of the Pacific and is dominated by warm air extrusions, whereas the second is placed northward of the exit region of the jet stream, where the meridional θ gradient is much weaker. Two European blocking types have been detected using the RI index, which separates out the cases dominated by warm and cold air masses. The latter cases in particular exhibited a well-structured dipole, with associated strong anomalies in both temperature and precipitation. Copyright © 2011 Royal Meteorological Society

Trinuclear and tetranuclear adduct formation between sodium perchlorate and copper(II) complexes of salicylaldimine type ligands: structural characterization and theoretical investigation

The synthesis of two new sodium perchlorate adducts (1:2 and 1:3) with copper(II) "ligand-complexes'' is reported. One adduct is trinuclear [(CuL(1))(2)NaClO(4)] (1) and the other is tetranuclear [(CuL(2))(3)Na]ClO(4)center dot EtOH (2). The ligands are the tetradentate di-Schiff base of 1,3-propanediamines and salicylaldehyde (H(2)L(1)) or 2-hydroxyacetophenone (H(2)L(2)). Both complexes have been characterized by X-ray single crystal structure analyses. In both structures, the sodium cation has a six-coordinate distorted octahedral environment being bonded to four oxygen atoms from two Schiff-base complexes in addition to a chelated perchlorate anion in 1 and to six oxygen atoms from three Schiff-base complexes in 2. We have carried out a DFT theoretical study (RI-B97-D/def2-SVP level of theory) to compute and compare the formation energies of 1:2 and 1:3 adducts. The DFT study reveals that the latter is more stabilized than the former. The X-ray crystal structure of 1 shows that the packing of the trinuclear unit is controlled by unconventional C-H center dot center dot center dot O H-bonds and Cu(2+)-pi non-covalent interactions. These interactions explain the formation of 1 which is a priori disfavored with respect to 2.

Wave-breaking characteristics of Northern Hemisphere winter blocking: a two-dimensional approach

This paper generalises and applies recently developed blocking diagnostics in a two- dimensional latitude-longitude context, which takes into consideration both mid- and high-latitude blocking. These diagnostics identify characteristics of the associated wave-breaking as seen in the potential temperature (θ) on the dynamical tropopause, in particular the cyclonic or anticyclonic Direction of wave-Breaking (DB index), and the Relative Intensity (RI index) of the air masses that contribute to blocking formation. The methodology is extended to a 2-D domain and a cluster technique is deployed to classify mid- and high-latitude blocking according to the wave-breaking characteristics. Mid-latitude blocking is observed over Europe and Asia, where the meridional gradient of θ is generally weak, whereas high-latitude blocking is mainly present over the oceans, to the north of the jet-stream, where the meridional gradient of θ is much stronger. They occur respectively on the equatorward and poleward flank of the jet- stream, where the horizontal shear ∂u/∂y is positive in the first case and negative in the second case. A regional analysis is also conducted. It is found that cold-anticyclonic and cyclonic blocking divert the storm-track respectively to the south and to the north over the East Atlantic and western Europe. Furthermore, warm-cyclonic blocking over the Pacific and cold-anticyclonic blocking over Europe are identified as the most persistent types and are associated with large amplitude anomalies in temperature and precipitation. Finally, the high-latitude, cyclonic events seem to correlate well with low- frequency modes of variability over the Pacific and Atlantic Ocean.

The gravity wave momentum flux in hydrostatic flow with directional shear over elliptical mountains

Semi-analytical expressions for the momentum flux associated with orographic internal gravity waves, and closed analytical expressions for its divergence, are derived for inviscid, stationary, hydrostatic, directionally-sheared flow over mountains with an elliptical horizontal cross-section. These calculations, obtained using linear theory conjugated with a third-order WKB approximation, are valid for relatively slowly-varying, but otherwise generic wind profiles, and given in a form that is straightforward to implement in drag parametrization schemes. When normalized by the surface drag in the absence of shear, a quantity that is calculated routinely in existing drag parametrizations, the momentum flux becomes independent of the detailed shape of the orography. Unlike linear theory in the Ri → ∞ limit, the present calculations account for shear-induced amplification or reduction of the surface drag, and partial absorption of the wave momentum flux at critical levels. Profiles of the normalized momentum fluxes obtained using this model and a linear numerical model without the WKB approximation are evaluated and compared for two idealized wind profiles with directional shear, for different Richardson numbers (Ri). Agreement is found to be excellent for the first wind profile (where one of the wind components varies linearly) down to Ri = 0.5, while not so satisfactory, but still showing a large improvement relative to the Ri → ∞ limit, for the second wind profile (where the wind turns with height at a constant rate keeping a constant magnitude). These results are complementary, in the Ri > O(1) parameter range, to Broad’s generalization of the Eliassen–Palm theorem to 3D flow. They should contribute to improve drag parametrizations used in global weather and climate prediction models.